CN1017145B

CN1017145B - Hydroformylation with low volatile phosphine ligands

Info

Publication number: CN1017145B
Application number: CN87101178A
Authority: CN
Inventors: 安东尼·乔治·阿贝佐劳; 戴维·罗伯特·布赖恩特
Original assignee: Union Carbide Corp
Current assignee: Union Carbide Corp
Priority date: 1986-11-18
Filing date: 1987-11-18
Publication date: 1992-06-24
Also published as: ES2012719A6; YU209187A; GB8727013D0; EP0268268B1; DE3739064A1; AR248390A1; NO874810D0; DK605887D0; FI90858C; AU8128087A; FI875087L; SE8704533D0; AU611867B2; FR2606771B1; EP0268268A3; NO166440B; YU45074B; IN170369B; RU2002728C1; NO874810L

Abstract

A non-aqueous hydroformylation process for producing aldehydes using low volatility, organically solubilized monosulfonated tertiary phosphine metal salt ligands.

Description

Hydroformylation using low volatile phosphine ligands

Transition metal-the phosphorus complex that the invention relates to single sulfonation tertiary phosphine metal salt ligands carries out catalytic hydroformylation.More particularly, the invention relates to rhodium-single sulfonation tertiary phosphine metal salt ligands complex catalysis the non-water hydroformylation of olefin(e) compound is generated corresponding aldehydes.

By being solubilized into organic transition metal-phosphorus co-ordination complex catalyzer, the hydroformylation of carrying out olefin(e) compound with carbon monoxide and hydrogen is that people are familiar with in the present technique field.

People also know, and whether the phosphorus part that is used for this process for catalytic hydroformylation successfully has a direct impact this method.But be used for the selection of the concrete phosphorus part of any this transition metal-catalyzed hydroformylation process, depend primarily on and require the net result that reaches, because the efficient of entire method need weighed between a large amount of related factors.For example, in aldehyde reaction, resemble aldehyde product selectivity (that is the ratio of n-alkanal and isomery aldehyde), catalyst activity and stability and part stability like this some factors often be the problem of major concern when selecting used satisfactory phosphorus part.For example, United States Patent (USP) 3,527 is pointed out for No. 809, and the selectivity hydroformylation of carrying out alpha-olefin with three organic phosphines or the three organic phosphorous acid co-ordination complexs of rhodium how is rich in the oxidation products of positive aldehyde with production; And United States Patent (USP) has been announced the liquids and gases return that reaches equifinality with the triaryl phosphine part complex catalyst of rhodium 4,148, No. 830 and 4,247, No. 486.United States Patent (USP) 4,283 announces that branched-chain alkyl phosphniline or cycloalkyl phosphniline part can be used for the catalytic hydroformylation process of rhodium No. 562, so that the catalyzer of more stable anti-intrinsic inactivation to be provided.United States Patent (USP) 4,400 has announced that two phosphine-monoxide ligands can be used for providing thermostability improved rhodium complex catalyst No. 548, is applicable to that hydroformylation produces aldehydes.

But although prior art above-mentioned brings significant benefits, people still continue to seek the phosphorus part that more effectively satisfies other requirement of part, particularly about the volatility of part.

For example, rhodium complex catalyzed hydroformylation process is preferably in the non-water aldehyde reaction medium and carries out, this medium contains olefinically unsaturated compounds, aldehyde product, by the catalyst complex of solubilising and excessive free phosphorus part, promptly do not connect or key is linked part on the rhodium complex.In such method, the required the most handy distillating method of aldehyde product separation and Extraction from the reactor product medium is come out, and is carrying out continuously under the situation of liquid catalyst return, and the resistates that contains non-volatile catalyzer one part returns and enters reactor.Correspondingly, an important requirement is to separate from aldehyde reaction product medium effectively and reclaim required aldehyde product to this method, and does not cause the excessive loss of phosphorus part and/or catalyst complex.Therefore, in this non-water hydroformylation process, particularly in the method that liquid catalyst returns, phosphorus part volatility also is the problem of major concern, because carrying out with distillating method in the process of aldehyde product separation, remove (stripping) phosphorus part continuously and not only can cause a large amount of losses (must replenish) of phosphorus part, and cause the variation of catalyst performance even finally make catalyst deactivation.In fact, if evaporable speed of this while of phosphorus part is too fast, then may need to add a part recovery/retrieval system again so that make process more economical.

Though with common tertiary phosphine, as triphenylphosphine, when low molecular weight olefins such as propylene were carried out non-water hydroformylation, part volatilization and aldehyde product separation problem were so not outstanding, ought carry out the long-chain olefin compound (as C ₈-C ₂₀When hydroformylation alkene) was produced corresponding high molecular weight aldehyde, it is big that this problem just becomes, and caused paid certain attention, because very high by the required temperature of these high molecular weight aldehyde of evaporation in the aldehyde reaction product medium.Need from the hydroformylation resistates that for example contains catalyzer, remove high boiling aldehyde condensation byproduct, as trimer etc., so that reclaim under the situation of catalyzer and part, because volatilization causes ligand loss to be still the problem of technology major concern, no matter this acetal byproduct is lower molecular weight (C for example ₂-C ₅) still be that high molecular is (as C ₆-C ₂₀) result of hydroformylation.

Someone advises with the sulfonate aryl phosphine compound aqueous solution as the phosphorus part, as No. 163234, European patent and United States Patent (USP) 4,248, No. 802,4, the sulfonated triphenylphosphine salt of announcement such as 399, No. 312 is cooked the phosphorus part in hydroformylation process, be beneficial to the separation and the recovery of rhodium complex catalyst.But all these prior arts will be used two-phase liquid equally, i.e. the heterogeneous aldehyde reaction medium of being made up of organic phase that contains respond starting raw material and/or product and the water that contains catalyst complex and sulfonated phosphine part.In addition, reactor pressure that this water hydroformylation system general requirement is higher and/or higher rhodium concentration to overcome aldehyde reaction inherent lower velocity, also may need buffer reagent or consisting of phase-transferring agent and/or bigger, more expensive treatment facility.

Therefore, in the hydroformylation technology, need the phosphorus ligand of low volatility certainly, so as promptly to low molecular weight olefins (as, C ₂-C ₅Alkene) again can be to long-chain particularly, high molecular weight olefin compound (as, C ₆-C ₂₀Alkene) in non-water rhodium process for catalytic hydroformylation, work effectively.

Have now found that single sulfonation tertiary phosphine metal salt ligands can be used as the phosphorus part in non-water the 8th group 4 transition metal-catalytic hydroformylation process of phosphorus complex, and has lot of advantages.

For example, here used single sulfonation tertiary phosphine metal salt ligands is water miscible, and they are insoluble in the nonpolar aldehydes of high molecular and/or the alkene particularly in most of aldehydes and/or alkene usually, perhaps be difficult to dissolving, therefore, be not suitable in the non-water hydroformylation process of rhodium catalysis, being used as the phosphorus part very much.But, have now found that, in the catalytic non-water aldehyde reaction medium of rhodium, by adding some organic solubilized agent and/or their mixture, the single sulfonation tertiary phosphine metal salt ligands that adopts can be converted into solubility here, therefore, can in this non-water rhodium catalysis process, be used.But also find that in some instances, some single sulfonation tertiary phosphine metal-salt just had enough solubleness originally in some non-water aldehyde reaction medium, so that can directly in the catalytic hydroformylation process of the non-water rhodium of this class, be used as the phosphorus part.

Be applicable to that the extremely low volatility of single sulfonation tertiary phosphine salt part of present method is highly beneficial to the hydroformylation technology of being discussed.For example, since this low volatility, the operation of from the reactor product medium that contains using rhodium complex catalysts, isolating the aldehyde product, and the method for available evaporation (distillation) is finished at an easy rate, even non-water hydroformylation process purpose is to produce high-molecular weight aldehyde product, for example by C ₆-C ₂₀The aldehydes that the long-chain olefin hydroformylation obtains, part and/or catalyzer do not have excessive loss yet.In addition, this single sulfonation tertiary phosphine metal salt ligands that is applicable to present method can be quickened lower molecular weight (C ₂-C ₄) and high molecular (C ₆-C ₂₀) the rhodium catalytic hydroformylation of alkene, even make it (for example, be lower than 500Psig(pound/inch at lower hydroformylation pressure usually ²Gauge pressure)) and/or when using low rhodium concentration, also can remain on complete acceptable catalytic activity speed, and don't too sacrifice the efficient of process and/or the stability of catalyzer.And, do not find the generation that the suitable single sulfonation tertiary phosphine metal salt ligands of present method can too and nocuously accelerate to produce the substandard goods aldehyde polymer.In addition, relate to the present invention of high molecular weight olefin hydroformylation, its non-water hydroformylation process can be under the situation of not doing great change, easily transforms and is adapted to equipment and device into existing non-water hydroformylation design, and these equipment and device are used for the hydroformylation of low molecular weight olefins usually in the past.

This another the unexpected advantage of single sulfonation tertiary phosphine metal salt ligands of the present invention that is applicable to is, the ratio (being selectivity) of this hydroformylation process straight chain (just) aldehyde and side chain (different) aldehyde product can change, method therefor changes the above-mentioned aldehyde product ratio except regulating carbon monoxide pressure of tension and/or ligand concentration, can also be as long as changed the metallic cation of these parts.Just this/different (N/I) optionally is controlled in the aldehyde reaction extremely important, and this just makes people can just in time gather any desired concrete aldehyde product ratio.In addition, this control that can change N/I aldehyde product ratio can be issued in the condition of reduction process efficiency within reason and/or catalyst stability.

Therefore, an object of the present invention is to provide an improved rhodium process for catalytic hydroformylation, wherein said method is carried out in non-water aldehyde reaction medium with low volatility list sulfonation tertiary phosphine metal salt ligands.Other purpose of the present invention and advantage will be realized that from hereinafter introduction and appended claim.

Correspondingly, the present invention generally speaking is, the non-water hydroformylation process of improvement of producing aldehyde, it be included in contain alkene unsaturated organic compound, aldehyde product, by the 8th group 4 transition metal of solubilising-phosphorus part complex catalyst with by in the reaction medium of the non-water hydroformylation of the free phosphorus part of solubilising, alkene unsaturated organic compound and carbon monoxide and hydrogen are reacted.Its improvement is, comprises and uses phosphorus ligand and the above-mentioned free phosphorus part of a kind of single sulfonation tertiary phosphine metal-salt as above-mentioned complex catalyst.The general formula of this single sulfonation tertiary phosphine metal-salt is

Wherein each R group is represented a group that contains 1～30 carbon atom respectively, and they are selected from this class group of alkyl, aryl, alkaryl, aralkyl and cycloalkyl; M represents to be selected from a kind of metallic cation in basic metal, the alkaline-earth metal; The value of n is 1 or 2, corresponding to the valence state of the concrete metallic cation of M representative.Here said aldehyde reaction medium also comprises the organic solubilized agent of at least a q.s, and it can make the 8th used group 4 transition metal-single sulfonation tertiary phosphine metal-salt ligand complex catalyzer and free list sulfonation tertiary phosphine metal salt ligands be dissolved in the above-mentioned aldehyde reaction medium; Here said organic solubilized agent is selected from molecular-weight average and is at least 150 alkylene oxide oligopolymer, molecular-weight average and is at least organic non-ionic surface activator single alcohol of 300 and molecular weight and is lower than 150 and Xi Erde Brant (Hildebrand) solubility exponent equals 10 polar organic compound and their mixture at least; Condition is in the aldehyde reaction medium, about 35% of the no more than above-mentioned medium-weight of amount of above-mentioned alkylene oxide oligopolymer, about 60% of no more than this medium-weight of amount of above-mentioned organic non-ionic surface activator single alcohol, about 60% of no more than this medium-weight of amount of above-mentioned polar organic compound; Other has supplementary condition to be, add in this medium organic solubilizing agent the no more than said medium-weight of total amount about 60%.

Correspondingly, content of the present invention is, reaction by means of olefinically unsaturated compounds and carbon monoxide and hydrogen, implement any known non-water hydroformylation process to produce aldehydes, be reflected in the non-water aldehyde reaction medium and carry out, wherein contain olefinically unsaturated compounds, aldehyde product, by the 8th group 4 transition metal of solubilising-phosphorus part complex catalyst with by the free phosphorus part of solubilising, wherein as disclosed in this invention, the phosphorus part of this catalyzer and free phosphorus part replace with single sulfonation tertiary phosphine metal ligand.This general non-water hydroformylation (oxo process) method is well-known in the present technique field, for example referring to United States Patent (USP) 3,527, and No. 809,4,148, No. 830,4,247, No. 486 etc.Therefore, reaction conditions of the present invention and operative technique when needed can be according to applied any known reaction conditions and operative techniquies in common this non-water aldehyde reaction so far.

For example, this aldehyde reaction can successive, and is semi-continuous, or mode intermittently carries out, and as requested, can comprise the return of any liquid and/or gas.Equally, add the mode and the order of the solubilizing agent of reactant composition, catalyzer, part and/or adding, can carry out in the mode easily of any hope.

As indicated, aldehyde reaction is carried out in non-water aldehyde reaction medium, wherein contains by the 8th group 4 transition metal of solubilising-single sulfonation tertiary phosphine metal salt complex catalyzer with by free single sulfonation tertiary phosphine metal salt ligands of solubilising." free ligand " be meant not with the activated complex catalyzer in the phosphorus part of the 8th group 4 transition metal atom complexing (be connected or key connects).In addition, the meaning of term used herein " non-water " is, hydroformylation process of the present invention is to carry out under anhydrous or substantially anhydrous situation, that is to say, any water if any, its content should be not enough so that this process or above-mentioned medium are considered to also comprise in addition an isolating water or water layer except that organic phase.

As noted above, be applicable to that single sulfonation tertiary phosphine metal salt ligands of the present invention is the part with following chemical formula

Wherein the definition of each R, n and M is said the same with the front.

The example of R base comprises in the chemical formula of top single sulfonation tertiary phosphine salt part, the monovalence alkyl that does not replace and replace that contains 1～30 carbon atom, for example, the alkyl of straight or branched, primary alkyl, secondary alkyl or tertiary alkyl, as: methyl, ethyl, n-propyl, sec.-propyl, butyl, sec-butyl, the tertiary butyl, tertiary butyl ethyl, tertiary butyl propyl group, n-hexyl, amyl group, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, 2-ethylhexyl, n-octyl, iso-octyl, decyl, dodecyl, octadecyl, eicosyl etc.; Aryl is as phenyl, naphthyl etc.; Aralkyl is as phenmethyl, styroyl, trityl ethyl etc.; Alkaryl is as tolyl, xylyl etc.; And alicyclic radical, as cyclopentyl, cyclohexyl, ring octyl group, cyclohexyl ethyl etc.In addition, these monovalence alkyl can be replaced by any substituting group, as long as the result of the unlikely excessive infringement the present invention expectation of these bases.The example of hydrocarbyl substituent can comprise for example silyl, as-Si(R ⁹) ₃; Amino, as-N(R ⁹) ₂; Acyl group, as-C(O) R ⁹; Acidic group, as-oc(O) R ⁹; Amide group, as-CON(R ⁹) ₂With-N(R ⁹) COR ⁹; Alkylsulfonyl, as-SO ₂R ⁹; Alkoxyl group, as-OR ⁹; Sulfinyl, as-SR ⁹; Phosphono, as-P(o) (R ⁹) ₂, and halogen, nitrogen, cyanogen, trifluoromethyl and hydroxyl etc., wherein each R ⁹TYP or different separately replacements or unsubstituted monovalence alkyl, its meaning and preamble definition R's is the same, and what need particularly point out is, the ammonia substituting group, as-N(R ⁹) ₂In, each R ₉Be connected together one two valence bridge formula group also can be provided, it and nitrogen-atoms form heterocyclic group, at amide substituents as-C(o) N(R ⁹) ₂And-N(R ⁹) COR ⁹In, the R of each and N key also can be a hydrogen.Certainly, each R group can be the same or different in the metal salt ligands that specifically provides, and this is self-evident.

The comparatively preferential monovalence alkyl of selecting of being represented by R is the straight or branched alkyl that contains 3～20 carbon atoms, the alicyclic radical that contains the aryl of 6～12 carbon atoms and contain 5～12 carbon atoms.Better choice is each a kind of naturally branched-chain alkyl, phenyl or cyclohexyl that contains 3～9 carbon atoms of each R group.And best choice be represent a phenyl and/or cyclohexyl, particularly phenyl for the R base in single sulfonation tertiary phosphine metal salt ligands.

As noted above, the M in single sulfonation tertiary phosphine metal salt ligands chemical formula represents a kind of metallic cation that is selected from basic metal and the alkaline-earth metal.Alkali-metal example comprises lithium (L ⁺ ₁), sodium (Na ⁺), potassium (K ⁺), caesium (Cs ⁺) and rubidium (Rb ⁺) and the example of alkaline-earth metal comprises: calcium (Ca ⁺), barium (Ba ⁺⁺), magnesium (Mg ⁺⁺) and strontium (Sr ⁺⁺).In addition, point out that as the definition of top n metal salt ligands can comprise 1 or 2 single sulfonation tertiary phosphine negatively charged ion, this equals the positive valence state of metallic cation M.The single sulfonation tertiary phosphine of a class of the present invention metal salt ligands that can be used for of higher preference is, wherein each R represents separately by the alkyl that contains 3～20 carbon atoms (the secondary branched-chain alkyl that particularly contains 3-9 carbon atom, as sec.-propyl, the tertiary butyl etc.), phenyl and cyclohexyl; M wherein and n then with above define identical.

The example of preferential single sulfonation tertiary phosphine metal salt ligands of selecting comprises the part of following general formula representative.See Fig. 1

Be applicable to that single sulfonation tertiary phosphine metal salt ligands of this class of the present invention and/or their manufacture method are known by people, for example, " JChem Soc ", the step that the 276th～288 page (1958) and United States Patent (USP) are told about for 4,483, No. No. 802.This part preferably will contain the phenyl of tertiary phosphine accordingly, for example

Wherein R and above-mentioned definition is identical, under the controlled temperature condition, carries out sulfonation with oleum and produces, and mainly generates the corresponding protonated single sulfonation phenyl that contains tertiary phosphine, as,

For example, temperature is controlled at below 30 ℃, and the solid phosphine is joined in the oleum in batches, and heating is for example arrived 70-80 ℃ then, and is no longer muddy until the sample of taking from reaction mixture.Then reaction mixture is cooled off immediately so that stop further sulfonation, and when being controlled at below 30 ℃, temperature immediately reaction mixture is poured in the water, then with of the oxyhydroxide neutralization of above-mentioned protonated phosphonium salt with a kind of corresponding high concentrated base metal or alkaline-earth metal, to generate the insoluble single sulfonation phenyl that wherein contains the tertiary phosphine metal salt precipitate in the corresponding water, for example

And metal sulfate byproduct.Filter then, again with methyl alcohol with tertiary phosphine metal monosulfonate throw out by extracting in the metal sulfate, revaporization falls methyl alcohol, promptly recyclable this throw out.If necessary, this tertiary phosphine metal monosulfonate raw product can be carried out purifying then, method is that it is dissolved in appropriate solvent such as water or the ethanol, again by carrying out recrystallization in the solution.Self-evident, the R in the chemical formula of front, M are the same with definition in the past with n.

Can be used to prepare the tertiary phosphine of single sulfonation tertiary phosphine metal salt ligands in the present invention and the example of metal hydroxides comprises: triphenylphosphine, diphenylcyclohexyl phosphine, phenyl dicyclohexylphosphontetrafluoroborate, phenylbenzene sec.-propyl phosphine, phenyl diisopropyl phosphine, phenylbenzene tertiary butyl phosphine, etc.; Lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, hydrated barta, calcium hydroxide, strontium hydroxide etc.And, if desired, can make neutralizing agent with the carbonate of corresponding alkali metal or alkaline-earth metal or supercarbonate and replace oxyhydroxide above-mentioned.

Be surprised to find that, use and add some special solubilizing agent, can make and be applicable to that single sulfonation tertiary phosphine metal salt ligands of the present invention and the 8th group 4 transition metal-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst are soluble in the organic system, therefore can be used in the aldehyde reaction medium of non-water, no matter be that this hydroformylation process is to carry out lower molecular weight C ₂-C ₅The alkene class still is high molecular C ₆-C ₂₀The hydroformylation of alkene class.

The front points out that this special organic solubilized agent additive comprises: the molecular-weight average minimum is that 150 alkylene oxide oligopolymer, molecular-weight average minimum are organic non-ionic surface activator single alcohol of 300 and molecular weight less than 150, Xi Erde Brant solubility exponent is at least 10 polar organic compound and their mixture.

Do not make this single sulfonation tertiary phosphine metal salt ligands and the 8th group 4 transition metal-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst though do not plan necessarily to get clear these special solubilizing agent, in non-water aldehyde reaction medium, become on the problem of solubility and how to work, but can think that these solubilizing agent that are soluble in non-water aldehyde reaction medium itself can be regarded as surrounds part salt and complex compound catalyst, therefore makes them dissolve in non-water aldehyde reaction medium.In other words, solubilizing agent can be regarded as and the coordination of part salt, forms a kind of complex compound that dissolves in non-water aldehyde reaction medium, equally also makes by this complex compound catalyzer that obtains of deriving also can be dissolved in above-mentioned reaction medium.

In any case, not rely on the special solubilizing agent of seeking adding be that largely insoluble part salt and catalyzer can be dissolved in the non-water aldehyde reaction medium in the present invention.As long as know, when also containing these special organic solubilized agent additives in the aldehyde reaction medium, part salt and just can in above-mentioned aldehyde reaction medium, dissolve this fact by its complex compound catalyst that obtains of deriving, just enough for purpose of the present invention.

Be applicable to that alkylene oxide oligopolymer of the present invention all is liquid or LMP solid, they become liquid under the temperature of reaction of hydroformylation process, and their molecular-weight average is greatly about 150～10, between 000, or bigger, they comprise as

The such oligopolymer of the how pure and mild cyclic polyolefine oxygen of formula polyalkylene oxide ether.The molecular-weight average of these oligopolymers is relatively good between 500～about 7000,500～about 2000 better.These compounds and their preparation method are known by people.The many alcohol of these chain polyalkylene oxides comprise poly-(alkylene oxide) ethylene glycol, the alkylene oxide derivatives of glycerol (also being called polyether triol usually), and functionality is greater than polyether polyol of three etc.These alcohols can be easy to buy from market according to the trade name of enumerating below: CARBOWAX

PEG, CARBOWAX

TPEG, NIAX

PPG and UCON

Liquid (being all Union Carbide Corporation's product) also has POLYGLYCOL-E

(making (Dow) chemical company), POLY-G

(Olympic (Olin) company), PLURACOL-E

(BASF-Huai Enduote (Wyandotte) company), JEFFOX

(company of Texaco (Texaco)) etc.Poly-(alkylene oxide) glycols that relatively is suitable for comprises by this base polymer of following chemical formula representative and their mixture:

Wherein X is an integer, R ²And R ³Can select hydrogen and methyl for use.Certainly in given compound, each R ²And R ³Group may be the same, also may be different.More suitable poly-(alkylene oxide) ethylene glycol can be selected poly-(ethylene oxide) ethylene glycol for use, poly-(third alkylene oxide) ethylene glycol and their mixture.The example of poly-(alkylene oxide) glycol comprises: CARBOWAX PEG-600, a kind of molecular-weight average are about 600 poly-(ethylene oxide) ethylene glycol, CARBOWAX PEG-150, a kind of molecular-weight average are about 150 poly-(ethylene oxide) ethylene glycol, NIAX

PPG-1025, a kind of molecular-weight average are about poly-(third alkylene oxide) ethylene glycol of 1025 etc.The polyalkylene oxide derivative example of the preferential glycerol of selecting comprises compound by following chemical formulation and composition thereof:

Wherein X is an integer, R ⁴And R ⁵Select hydrogen and methyl for use.Certainly, each R in the given compound ⁴And R ⁵Can identical also possibility difference.The glycerol polyalkylene oxide derivative of more preferential selection is a glycerol polyethylene oxygen derivative, as CARBOWAX

TPEG-990, a kind of molecular-weight average are about 990 glycerol polyethylene oxygen derivative.Be applicable to that cyclic polyolefine oxygen ethers of the present invention comprises United States Patent (USP) 4,162, No. 261 said crown ethers.Crown ether and/or its manufacture method people are very familiar.Thereby the crown ether of Shi Yonging mainly contains carbon, hydrogen and oxygen and can be called monocycle and many rings herein.Can not there be the aldehyde atom of remarkable contribution also may exist on a small quantity to the solvency action of crown ether according to the present invention.Generally, contain 4 Sauerstoffatoms in the crown ether main ring at least, each Sauerstoffatom is belonged to carbon atom by the fat of at least two serial connections and separates.Preferably, contain at least two epoxy atom that link to each other with ethene or substituted ethylene base on the main ring.Other Sauerstoffatom or link to each other on the main ring with propylidyne, butylidyne, replacement propylidyne, perhaps with replace butylidyne and link to each other, perhaps be connected with their mixture.The brief feature of this class crown ether and more detailed description can find in No. 4,162,261, above-mentioned United States Patent (USP).This paper that is disclosed in detail of this patent quotes in the mode of reference.No more than 50 of the crown ether of selecting for use contained ether oxygen atom in main ring, it is more suitable to contain 4-15 ether oxygens atom on the main ring.And, because the monocycle crown ether is easy to preparation, so the most suitable.The specific examples of crown ether has 15-hat-5 described in No. 4,162,261, the above-mentioned United States Patent (USP) and 18-hat-6 etc.

Be applicable to that organic non-ionic surface activator single alcohol of the present invention is that molecular-weight average is at 300-5000(or bigger) liquid in the scope, more suitable molecular-weight average comprises the surfactant that resembles alcoxyl alcohol and so between 500～2000.These compounds and preparation method thereof people all know, for example at United States Patent (USP) 4,453, can find in No. 022, and the whole of this patent are disclosed in herein as reference citation.This alcoxyl alcohol is the product of monohydroxy alkylate or alkane substituting phenol and alkylene oxide reaction, and said here alkyl can contain 4～25 carbon atoms.Certainly, should be understood that this class monohydroxy alkylate except that every kind of single alcohol, also may be with the mixture of common currently known methods by the single alcohol of fat that obtains in petroleum mixture or natural fat and the oils.The example of alcoxyl alcohol comprises alcoxyl alcohol and their mixture by following chemical formula representative:

Wherein X represents an integer, R ⁶Be fats primary, the second month in a season and branched-chain alkyl, alkylphenyl group and their mixture, R ⁷And R ⁸Select hydrogen or methyl for use.Certainly, in a given alkoxide, each R ⁷And R ⁸Group may be identical, also may be different.R ⁷And R ⁸Hydrogen preferably, alcoxyl alcohol is ethoxy alcohol preferably.

Be applicable to alcoxyl alcohol of the present invention, promptly contain the group that water-soluble (polarity) also contains oil soluble (nonpolar), they are easy to buy with following trade name on market: TERGITOLS(Union Carbide Corporation), general aniline of IGEPALS(and film company, GAF Corp), ALFONICS(Ke Nuoke (Conoco) company), BRIJ(ICI company), NEODOLS(shell chemical company), STANDAMULS(Henkel (Henkel) company), chemical company of SURFONICS(Texaco (Texaco)), TRITONS(rom-Haas (Rohm ﹠amp; Hass) company) etc., these alcoxyl alcohol are for example at United States Patent (USP) 4,453, " chemical technology complete works " (1983) third edition of No. 022 and Kiel Ke-Ao Temo (Kirk-Othmer), and 22 volumes are announced on the 338-339 page or leaf.The TERGITOLS that the general formula representative of for example available following alcoxyl alcohol is relatively arranged in the alcoxyl alcohol of Shi Yonging:

R wherein ⁶With X as defined above, provided example in the table 20.

Also can be used as the polar organic compound of special organic solubilized agent additive of the present invention, comprise molecular weight less than 150 and Xi Erde Brant solubility exponent be 10 or higher organic liquid and their mixture.The example of this class polar compound (its Xi Erde Brant solubility exponent is write simultaneously) comprises low-carbon alcohol, as methyl alcohol (12.9), ethanol (11.2), propyl alcohol (10.2), Virahol (10.2) etc.; Also has nitrile, as cyanobenzene (10.7), acetonitrile (11.8), propionitrile etc.; N, the two substituted amide classes of N-, as dimethyl formamide (11.5), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone (14.8) etc.; The sulfoxide class is as dimethyl sulfoxide (DMSO) (12.8) etc.; The sulfone class, as dimethyl sulfone, sulfolane etc.; And other similar compound.Xi Erde Brant solubility exponent is a kind of experience yardstick of organic compound relative polarity, in some books argumentation is arranged, as: LRSnyder and JJKirkland work, (the John Wiley of Wiley-Interscience publishing company; Sons) " the modern liquid chromatography introduction " of Chu Baning, " solubleness of nonelectrolyte " that 215～218 pages (1974) and JHHildebrand and RLScott work, New York Dover publishing company publish, 424-434 page or leaf (1964).

Point out that above three different classes of special organic solubilized agent additives are arranged, that is, and (a) oligopolymer of alkylene oxide; (b) organic non-ionic surface activator single alcohol and (c) can be used for polar organic compounds of the present invention.In addition, as what also once pointed out, every compounds can use separately (promptly, one or more different solubilizing agent in the similar compound), perhaps the mixture of two or more inhomogeneity compounds (be solubilizing agent different in one or more similar compounds with at least a or multiple other at least one class or two compounds in different solubilizing agent together) also can be used for any given hydroformylation process of the present invention.Certainly, self-evident is no matter the compound of this classification is independent use, still mix and use, the total add-on of special organic solubilized agent in the non-water aldehyde reaction medium of given process, only need reach and to make used single sulfonation tertiary phosphine metal salt ligands and derive by it that to be dissolved in the desired minimum quantity of non-water aldehyde reaction medium relatively good for the complex compound catalyst that obtains, though used very big excessive also not seeing to do what its benefit like this.So, use separately as same compounds no matter be, still use as the part of inhomogeneity mixture, the consumption of alkylene oxide oligopolymer solubilizing agent of the present invention can about non-water aldehyde reaction medium-weight 1～35% between between (preferably in about 1～30%(weight)); And the consumption of organic non-ionic surface activator single alcohol solubilizing agent of the present invention can about non-water aldehyde reaction medium-weight 1～60% between between (being preferably in about 1～50%(weight)); And the consumption of polar organic compounds solubilizing agent of the present invention can about non-water aldehyde reaction medium-weight 1～60% between between (being preferably in about 1～35%(weight)).When with two or more inhomogeneity solubilizing agent compounds, total consumption of these solubilizing agent does not surpass 60% of non-water aldehyde reaction medium-weight in the said mixture, preferably is no more than 50%(weight).Certainly, be to be understood that, the highest consumption of above-mentioned every class solubilizing agent, and the highest consumption of the mixture of two or more inhomogeneity solubilizing agent compounds, it is the amount of the solubilizing agent that (being reactor media) exists in the aldehyde reaction medium corresponding to process, rather than corresponding to the amount that may be present in liquid circulation medium in the successive processes, this circulatory mediator can thicken because for example the desired product aldehyde of a part is extracted to recycle.It is also to be understood that, during the process if needed and when needed, for example, replenishing part to process or/and during catalyzer, if above-mentioned every class solubilizing agent, when not surpassing highest level, in carrying out, process can add this special solubilizing agent, so that in whole process, make solubilizing agent maintain desired level with the amount of any mixture of two or more inhomogeneity solubilizing agent.In addition, the mode and the order that this special solubilizing agent are joined non-water aldehyde reaction medium are not strict, although the process that generally is preferably in is added to reactor with metal salt ligands and complex catalyst the same manner at the very start.

Also be surprised to find that, some single sulfonation tertiary phosphine metal salt ligands and corresponding the 8th group 4 transition metal-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst thereof at lower molecular weight aldehyde (as, C ₃～C ₈) in enough organic solubles are arranged so that can directly apply to the same product of production in this non-water aldehyde reaction, and not need to add again any special solubilizing agent.For example, find single sulfonated phosphine metal-salt, quite big as sodium salt, lithium salts and rubidium salt solubleness in so low-molecular-weight aldehydes.If required, they are used in the condition of no longer adding this special solubilizing agent to get off to carry out low molecular weight olefins (are C ₂～C ₅) hydroformylation.And, lower concentration (as, be lower than 2%(weight)) the phosphine crown cap part that contains single sulfonation cyclohexyl, do not needing to add under the situation of any special solubilizing agent to lower molecular weight (C ₂～C ₅) and high molecular (C ₆～C ₂₀) hydroformylation of olefins of great use.But it seems that this class example be kind of an exception, rather than rule.

Therefore, on the other hand, the present invention can be described as a kind of nonaqueous phase hydroformylation process of improved production aldehydes, this method be included in contain alkene unsaturated organic compound, aldehyde product, by the 8th group 4 transition metal of solubilising-phosphorus part complex catalyst and by in the non-water aldehyde reaction medium of the free phosphorus part of solubilising, allow the alpha-olefin that contains 2～5 carbon atoms and carbon monoxide and hydrogen react, its improvement is to adopt phosphorus part and the above-mentioned free phosphorus part of a kind of single sulfonation tertiary phosphine metal-salt as above-mentioned catalyzer, and the general formula of this metal-salt is as follows:

Wherein M represents to be selected from sodium, a kind of metallic cation of lithium and rubidium, the organic solvent of said here complex compound catalyst and said free ligand can be selected aldehyde for use, the mixture of high boiling point aldehyde condensation byproduct and they, said here hydroformylation process are that (they are selected from molecular-weight average and are at least 150 alkylene oxide oligopolymer not adding any organic solubilized agent, molecular-weight average is at least organic non-ionic surface activator single alcohol of 300, molecular-weight average less than 150 and Xi Erde Brant solubility exponent be at least 10 polar organic compound, and their mixture) carries out under the situation.

Again on the one hand, the present invention can be described as a kind of non-water hydroformylation process of improved production aldehydes, this method is included in and contains alkene unsaturated organic compound, aldehyde product, by the 8th group 4 transition metal of solubilising-phosphorus part complex catalyst with in the non-water aldehyde reaction medium of the free phosphorus part of solubilising alkene unsaturated organic compound and carbon monoxide and hydrogen are reacted, its improvement is, adopts a kind of general formula to be

Single sulfonation tertiary phosphine metal-salt as the phosphorus part and the above-mentioned free phosphorus part of above-mentioned complex compound catalyst, one of them R group is represented a cyclohexyl and another R group is represented phenyl or cyclohexyl, M represents to be selected from a kind of metallic cation of basic metal or alkaline-earth metal, the valence state of the concrete metallic cation that the n value will be represented according to M, its value is 1 or 2; The organic solvent of wherein above-mentioned complex compound catalyst and above-mentioned free ligand can be selected aldehyde, high boiling point aldehyde condensation byproduct and their mixture for use, wherein above-mentioned hydroformylation process carries out under without any the situation of organic solubilized agent, these solubilizing agent can select for use molecular-weight average be at least 150 alkylene oxide oligopolymer, molecular-weight average be at least organic non-ionic surface activator single alcohol of 300, molecular-weight average less than 150 and uncommon Er Delante solubility exponent be at least 10 polar organic compound and their mixture.

Also to point out, be surprised to find that the molecular weight of aldehyde product directly has influence on the lyotropy of the 8th group 4 transition metal of single sulfonation tertiary phosphine metal salt ligands used herein and/or its correspondence-single sulfonation tertiary phosphine metal salt complex catalyzer.Obviously, molecular weight has determined the polarity of aldehyde, has determined the solubility property of aldehyde to the complex compound catalyst of above-mentioned metal salt ligands and/or their correspondences thus again.For example, lower molecular weight aldehyde is (as C ₃～C ₆) than high molecular weight aldehyde (as C ₇～C ₂₁) polarity strong.For example, butyraldehyde is more a lot of by force than aldehyde C-9 polarity, therefore, for example can make single sulfonated triphenylphosphine sodium salt part solubilising to higher concentration.

Therefore, when the alkylene oxide oligopolymer of preamble narration was suitable for use as the special solubilizing agent of the present invention, if adopt high salt concn, the many alkoxide solutions of oligopolymer were easy to become strong polarity, and can form independent transparent liquid layer (that is second organic phase) with nonpolar aldehyde such as aldehyde C-9.Therefore, if think to obtain in this case and keep a single-phase homogeneous solution, can outside the many alcohol of said alkylene oxide oligopolymer, add a kind of special solubilizing agent or their mixture again, as previously mentioned, solubilizing agent can be selected organic non-ionic surface activator single alcohol and polar organic compound for use.

Single sulfonation tertiary phosphine metal salt ligands solution in organic non-ionic surface activator single alcohol that the present invention adopts, generally be easy to and fully with in addition nonpolar aldehydes (as aldehyde C-9) miscible, therefore, can make the solubleness of single sulfonation tertiary phosphine metal-salt than high a lot of in alkylene oxide oligopolymer.And this non-ionic surface activator single alcohol can play synergy with alkylene oxide oligopolymer, if both are when using together, plays solublization under the higher metal salt ligands concentration of the concentration that can reach than the every compounds of independent use the time.

Though above-mentioned polar organic compound solubilizing agent also can easily be used for making single sulfonation tertiary phosphine metal salt ligands to carry out solubilising in polarity and nonpolar aldehydes, but a shortcoming when using this class polar organic compound is a high volatility, and these are different with above-mentioned alkylene oxide oligopolymer and/or non-ionic surface activator single alcohol.This strong volatility can cause the stripping of polar organic compound when catalyzer-aldehyde product separation, can cause the ligand catalyst precipitation again.Therefore, when being used in operate continuously separately, the used in amounts of polar organic compound will carefully be monitored and replenish during the course.But, when using with nonvolatile alkylene oxide oligopolymer and/or nonvolatile non-ionic surface activator single alcohol, above-mentioned polar organic compound can increase the concentration solubleness of metal salt ligands in the mixture of alkene and polarity or nonpolar aldehydes greatly.

Certainly, another self-evident problem is, be applicable to the present invention and in alkylene oxide oligopolymer that preamble is illustrated and organic non-ionic surface activator single alcohol, contain alkylene oxide condensate, for example, under the situation of alkylene oxide oligopolymer, ethylene oxide is arranged, the mixture of third alkylene oxide or both mixtures and ethylene glycol (or glycerol), or under non-ionic surface activator single alcohol situation, have alcohol condenses, in addition, common preparation method often causes producing the mixture of high molecular condenses, comprising the multiple ethylene glycol of different alkylene oxide molecular ratios, the derivative of glycerol or alcohols.Therefore, the product compound that obtains is actually a kind of derivative that contains ethylene glycol, glycerol or the alcohol moiety of differing molecular ratio alkylene oxide unit.In addition, under the situation of alcoxyl alcohol, alcohol moiety itself can be derived by one or more alcohol and be obtained, for example, and C ₁₁～C ₁₅The mixture of alkyl alcohol.Therefore, as known to, about being present in the common number of alkylene oxide unit number in alkylene oxide oligopolymer or the alkyl alcohol molecule (X in the how pure and mild alcoxyl alcohol of the above-mentioned alkylene oxide oligopolymer chemical formula) is the mean number of alkylene oxide unit in each molecule of expression, and the alkylene oxide unit number in most of alkylene oxide oligopolymer or the alcoxyl alcohol all is greater than or less than this mean value that X represents.So mark of these products is all very familiar to the present technique field, and its meaning is also with customary consistent.

The transition metal that forms metal of the present invention-single sulfonation tertiary phosphine salt ligand complex comprises rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os) and their mixture, that more suitable is Rh, Co, Ir and Ru, preferably use Rh and Co, particularly Rh.Should be pointed out that success of the present invention is actual and do not rely on the real structure of catalytically-active metals complex compound, can not predict that these complex compounds may exist with monokaryon, double-core or multinuclear form according to this structure.In fact, real active structure it be unclear that.Though do not plan here to discuss what theory or mechanism, it seems the simple form of active catalytic complex compound, may be mainly connect and compose by carbon monoxide and single sulfonation tertiary phosphine metal salt ligands and the 8th group 4 transition metal complexing.

Here with claim in the term " complex compound " that uses refer to, a kind of by self-existent electron rich molecule of one or more energy or atom, and also can self-existent one or more electron-deficient molecules or the coordination compound that forms of atom.Can infer by above discussion, carbon monoxide (also can classify as part) exist equally and with the 8th group 4 transition metal complexing.The final composition of activated complex catalyzer also may comprise an organic ligand or negatively charged ion such as hydrogen etc. in addition again to satisfy the ligancy or the nuclear charge of the 8th group 4 transition metal, as former common situation about the 8th group 4 transition metal-three organic phosphine or phosphite catalysts.Will of course be appreciated that activated complex does not preferably contain any additional organic ligand or the negatively charged ion that perhaps can make poisoning of catalyst and undue infringement catalyst performance.For example, known usually in the catalytic aldehyde reaction of rhodium, halide anion can make poisoning of catalyst.Therefore, in rhodium catalytic hydroformylation reaction of the present invention, the halogen that active catalyst does not preferably contain directly and the rhodium key connects.

As everyone knows, the ligancy that can be occupied on this 8th group 4 transition metal is between 4～6.It seems according to example, the simple form of active phodium catalyst of the present invention preferably, total amount is single sulfonation tertiary phosphine metal salt ligands and carbon monoxide and 1 mole of rhodium complexing of 4 moles.Therefore, this active specy may be a kind of complex catalysis agent composition, exists with monokaryon, double-core or multinuclear form, it is characterized by each rhodium atom and one, two and/or three single sulfonation tertiary phosphine metal-salt molecular complex.As mentioned above, in the active specy carbon monoxide same exist and with the rhodium complexing.And, situation with common rhodium-three organic phosphine or phosphite ester ligand complex catalysis aldehyde reaction the same (it is generally acknowledged that active catalyst species wherein contains direct key and links hydrogen on the rhodium), the active specy of the present invention's used best rhodium catalyst in hydroformylation process except that with single sulfonation tertiary phosphine metal-salt and the complexing of carbon monoxide part, be considered to too with the hydrogen complexing.In fact can believe that any the 8th group 4 transition metal activity of such catalysts species of the present invention also can contain hydrogen except that containing single sulfonation tertiary phosphine metal-salt and carbon monoxide in hydroformylation process, particularly consider in this process and will use hydrogen.

In addition,, still in hydroformylation process, generate active specy on the spot, always aldehyde reaction is finished in the presence of free list sulfonation tertiary phosphine metal salt ligands no matter be to make active catalyst in the past entering the carbonylation reaction district.Therefore, according to example, the final composition of optimum activity using rhodium complex catalysts can be tied to or depend on carbon monoxide and single sulfonation tertiary phosphine metal salt ligands, and the result of competing reaction takes place for contention and rhodium element complexing or coordinate position.These competing reactions can in very large range be subjected to the role and influence of single sulfonation tertiary phosphine metal salt ligands concentration increase and decrease.In general, the competing reaction equilibrated is moved has more opportunity to occupy coordination or complexing position to own favourable person.For example, can or regard the present situation that in hydroformylation process, keeps the various forms of activated complex catalyzer as the effect of free list sulfonation tertiary phosphine salt part, make the mobile of competitive equilibrium thereby perhaps regard as, may from complex compound catalyst, drive away the carbon monoxide of approximately same quantity simultaneously own favourable more single sulfonation tertiary phosphine metal salt ligands and the rhodium complex coordination of making.

As noted above, both as the phosphorus part of the 8th group 4 transition metal complex catalyst, also conduct is present in the free phosphorus part in the inventive method reaction medium to single sulfonation tertiary phosphine metal salt ligands defined above in the present invention.In addition, also will be appreciated that, though the 8th group 4 transition metal in the given method of the present invention-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst and excessive free list sulfonation tertiary phosphine metal salt ligands are normally with a kind of, but the mixture of different single sulfonation tertiary phosphine metal salt ligands and two or more different single sulfonation tertiary phosphine metal salt ligands, if needed, in any given method, can be used for various purposes.

The same with the prior art situation, the 8th group 4 transition metal-phosphorus complex catalyst, existent method is synthesized on the 8th group 4 transition metal of the present invention-all available Technology of single sulfonation tertiary phosphine metal salt ligands complex compound catalyst.For example, can prepare preformed the 8th group 4 transition metal hydrogenized carbonyl list sulfonation tertiary phosphine metal salt ligands complex compound catalyst, it can be added in the reaction medium of hydroformylation process together with a kind of special organic solubilized agent of having said here if necessary.Preferably, the 8th group 4 transition metal of the present invention-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst can obtain from a kind of metal catalyst parent, parent can be joined in the reaction medium, generates active catalyst on the spot.For example, dicarbonyl rhodium acetylacetonate, Rh ₂O ₃, Rh ₄(CO) ₁₂, Rh ₆(CO) ₁₆, Rh(NO) ₃And so on the catalyst Precursors of rhodium, can be added to together in the reaction medium with above-mentioned single sulfonation tertiary phosphine metal salt ligands and a kind of special organic solubilized agent additive (if necessary), generate active catalyst on the spot.One preferably in the embodiment; dicarbonyl rhodium acetylacetonate is as the parent of rhodium; and in the presence of above-mentioned solubilizing agent (if necessary); generate a kind of rhodium carbonyl list sulfonation tertiary phosphine metal-salt Acetyl Acetone parent that catalytic performance is arranged with single sulfonation tertiary phosphine reacting metal salt, it is to be added to together with excessive free single sulfonation tertiary phosphine metal salt ligands and above-mentioned organic solubilized agent (if necessary) to generate active catalyst in the reactor on the spot.In any case, about purpose of the present invention, as long as knowing carbon monoxide, hydrogen and single sulfonation tertiary phosphine metal-salt all is the part that can carry out complexing with the 8th group 4 transition metal such as rhodium, and it is just enough to exist activated the 8th group 4 transition metal-such two facts of single sulfonation tertiary phosphine metal salt ligands complex compound catalyst under the condition of hydroformylation process in the reaction medium.

In addition, obviously, the same with ligand complex catalyzed dose of the 8th group 4 transition metal phosphorus in the prior art, its quantity of complex catalyst that exists in the given method aldehyde reaction of the present invention medium only require can make reach desired level for the 8th group 4 transition metal concentration minimum quantity, this concentration level can make the 8th group 4 transition metal reach essential to a catalytic hydroformylation process at least fundamental quantity.For most of hydroformylation process, if calculate with the free metal, the concentration of the 8th group 4 transition metal is generally just enough between about 10～1000PPm.In addition, in the rhodium catalytic hydroformylation process of the present invention, generally be more prone to adopt the rhodium (calculating) of 10～800PPm by the free metal.

The olefin feedstock reactant of the inventive method can be that the end is unsaturated or inner undersaturated, can be straight chain, side chain or ring texture.These alkene classes can contain 2～20 carbon atoms and can contain one or more unsaturated thiazolinyls.And these alkene classes can comprise group or the substituting group that hydroformylation process is not had extensive damage, for example: carbonyl, carbon acyloxy, oxygen, hydroxyl, oxo carbonyl, halogen, alkoxyl group, aryl, alkylhalide group etc.The example of olefinically unsaturated compounds comprises: alpha-olefin, internal olefin, olefin(e) acid alkane ester, olefin(e) acid alkene ester, alkene alkane ether, enol etc., for example: ethene, propylene, 1-butylene, the 1-amylene, the 1-hexene, the 1-heptene, the 1-octene, the 1-nonene, 1-decene, the 1-hendecene, the 1-laurylene, the 1-tridecylene, 1-tetradecylene, 1-ten pentaenes, the 1-hexadecylene, 1-17 alkene, the 1-octadecylene, 1-19 alkene, the 1-icosa alkene, 2-butylene, 2-methacrylic (iso-butylene), the 2-octene, vinylbenzene, 3-benzene-1-propylene, 1, the 4-hexadiene, 1, the 7-octadiene, 3-cyclohexyl-1-butylene, vinyl carbinol, oneself-1-alkene-4-alcohol, suffering-1-alkene-4-alcohol, vinyl acetate, allyl acetate, propionate, allyl propionate, allyl butyrate, methyl methacrylate, EVE, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octene ester, the 3-crotononitrile, 5-hexene acid amides etc.People know that certainly when needing, the mixture of different alkene class raw materials also can be used for hydroformylation process of the present invention.The present invention is suitable for producing aldehydes with the hydroformylation process that to contain the alpha-olefin of 2～20 carbon atoms and these alhpa olefins and interior alkene mixture be raw material especially.Suitable olefin feedstock is the lower molecular weight alhpa olefin that contains 2～5 carbon atoms, and that the high molecular alhpa olefin that contains 6～20 carbon atoms particularly contains the high molecular alhpa olefin of 6～14 carbon atoms is better.Certainly should understand, contain in the commodity alhpa olefin of 4 or 4 above carbon atoms and may also contain the interior alkene of a small amount of correspondence and/or the stable hydrocarbon of their correspondences, and these commodity alkene not need to carry out purifying before being used for the present invention.

As mentioned above, hydroformylation process of the present invention be to allow alkene unsaturated organic compound and carbon monoxide and hydrogen react, be reflected in the non-water aldehyde reaction medium and carry out, wherein contain alkene unsaturated organic compound, aldehyde product, by the 8th group 4 transition metal of solubilising-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst with by free single sulfonation tertiary phosphine metal salt ligands of solubilising, be a kind of special organic solubilized agent additive or their mixture of preamble definition for this catalyzer and the best organic solubilized immunomodulator compounds of free ligand.And, here used above-mentioned non-water aldehyde reaction medium, no matter present one or more organic phases, all be defined as the medium in this process reaction container (reactor), this reaction medium also can contain on the spot the high boiling point aldehyde condensation liquid by product that (for example, in continuous hydroformylation process) generates.Though this aldehyde condensation by-product may not be present in the reaction medium of intermittent process, and when beginning, successive processes also not necessarily exists, but this medium finally contains aldehyde product and high boiling point aldehyde condensation liquid by-product usually always, and this is that character by successive processes is determined.For example, aldehyde condensation byproduct and aldehyde product help to play by the catalyzer of solubilising with by the effect of the liquid phase carrier of the part of solubilising together in continuous liquid catalyst circulation hydroformylation process.If needed, the also available common mode of this class aldehyde condensation byproduct is as the thinner of process starting stage for example, and their preparation method has sufficient elaboration in United States Patent (USP) for example 4,148, No. 830 and 4,247, No. 486.Everybody also can know, when needed, can select the organic thinner that the hydroformylation process of the present invention that will carry out is not had very big evil for use, they may reside in the aldehyde reaction medium, for example, when crossing commencement of works, the concentration that helps to add special solubilizing agent in the aldehyde reaction medium maintains low-level.The most suitable thinner comprise with the hydroformylation process that will carry out in issuable aldehyde product and/or corresponding aldehyde of high boiling point aldehyde condensation by-product and/or high boiling point aldehyde condensation by-product, although any suitable he plants aldehydes and/or high boiling point aldehyde condensation by-product also can be used as this thinner.For example, Texanol (Yi Siman (Eastman) chemical products company), a kind of 2,2,4-trimethylammonium-1,3-pentanediol list isobutyl ester trimer is a kind of thinner easily of producing butyraldehyde.

And, as mentioned above, in some cases, some single sulfonation tertiary phosphine metal salt ligands and corresponding the 8th group 4 transition metal-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst thereof, can in these aldehyde and/or high boiling point aldehyde condensation by-product, have enough solubleness, so that can under the situation that does not have any special solubilizing agent additive, be directly used in non-water hydroformylation process.In these cases, aldehyde itself and/or their high boiling point aldehyde condensation by-product can be used as the organic solvent of single sulfonation tertiary phosphine metal salt ligands and corresponding complex catalyst thereof.At last, high boiling point aldehyde condensation byproduct and/or also may be present in organic thinner in the aldehyde reaction medium of the present invention, mainly only be subjected to given aldehyde reaction medium require to be present in wherein catalyzer and the addition of the required special organic solubilized agent of part control.Therefore, the high boiling point aldehyde condensation byproduct that non-water aldehyde reaction medium of the present invention preferably mainly contains olefin feedstock, aldehyde product, can not add by the 8th group 4 transition metal of solubilising-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst, by free single sulfonation tertiary phosphine metal salt ligands of solubilising, special organic solubilized agent additive and Ke Jia, and in some cases, this non-water aldehyde reaction medium even do not add any this special organic solubilized agent.

Generally, also more wish to carry out in a continuous manner this hydroformylation process of the present invention.This successive processes is all familiar in the present technique field, it can comprise, for example, in a non-water hydroformylation medium, allow olefin feedstock and carbon monoxide and hydrogen react, contain alkene, aldehyde product as mentioned above in the reaction medium, by the 8th group 4 transition metal of solubilising-single sulfonation tertiary phosphine metal salt ligands complex compound catalyst, by free single sulfonation tertiary phosphine metal salt ligands of solubilising and a kind of special organic solubilized agent additive (words if necessary); In reaction medium, supply with olefin feedstock, carbon monoxide and the hydrogen of magnitude of recruitment; Keep the temperature of reaction and the pressure condition that help hydroformylation; Usual method with any requirement reclaims desired hydroformylation product.Though successive processes can the one way mode be carried out, promptly, the vapour mixture of the aldehyde product that will contain the unreacted alkene raw material and be evaporated is by taking out in the liquid phase reaction medium, therefrom reclaim the aldehyde product, the restock olefin feedstock, carbon monoxide and hydrogen are fed in the liquid reaction medium that carries out next one way reaction and go, and the circulation of unreacted alkene raw material are not gone back, but the general successive processes of still wishing to adopt with liquid and/or gas circulation operation.Certainly, should be understood that the successive processes inconvenience that includes only the gas circulation operation is used to resemble the hydroformylation of the macromole alkene class that contains 6～20 carbon atoms, because aldehyde product volatility at this moment is low.The technical people of this circulating process are familiar, it can return in liquid circulation, and the 8th group 4 transition metal that will separate from the reactor product aldehyde of needs-single sulfonation tertiary phosphine metal salt ligands complex catalysis agent solution returns, it or can possess the gas circulation operation, perhaps comprise liquids and gases circulating process both (words if needed), for example United States Patent (USP) 4,148, No. 830,4,247, No. 486 and 4,593, No. 127 disclosed such.The best hydroformylation process of the present invention comprises the working cycle of a successive liquid rhodium catalyst.

Desirable aldehyde product can be with any method commonly used, and for example United States Patent (USP) 4,148, and No. 830,4,247, No. 486 and 4,593, that introduces for No. 127 reclaims like that.For example, in a continuous liquid catalyst working cycle, can deliver to evaporation/separator by the liquid-phase reaction solution part (containing aldehyde product, catalyzer etc.) that reactor takes out, under normal pressure, decompression or pressurized conditions, by single-stage or multistage distillation, the aldehyde product that requires is separated from liquid reaction solution, collected after the condensation in the product susceptor, be further purified again if needed.Remaining contains the liquid reaction solution of non-volatile catalyzer then, wherein also contains some aldehyde products and high boiling point aldehyde condensation byproduct, free phosphine liquid and special organic solubilized agent usually, the reactor of getting back to capable of circulation.Having under the situation about needing, separating from the aldehyde product of condensation with the ordinary method distillation, also be dissolved in any other volatile matter in the liquid reaction solution later on, for example not reacted alkene, hydrogen, carbon monoxide also turn back in the reactor.If not water aldehyde reaction medium forms two organic liquid layers, cause the catalyzer (rhodium, part and organic solubilized agent) of bottom and aldehyde product, some aldehyde condensation by-product that may exist and the two stratified word of unreacted alkene on upper strata, the aldehyde product that then needs also can be used the way of two organic phases of simple separation, for example, the method that decant goes out the aldehyde gas producing formation reclaims, and need not distill.At present, more wish in decompression and suitable temperature to be preferably in below 200 ℃ as below 250 ℃, with the method for evaporation from the product solution of rhodium-containing catalyst, isolate need the aldehyde product.

As mentioned above, hydroformylation process of the present invention is that free list sulfonation tertiary phosphine metal salt ligands is being arranged, promptly not and the part of the 8th group 4 transition metal complexing of used metal complex catalyst, carry out under existing, these free list sulfonation tertiary phosphine salt parts can be any above-mentioned single sulfonation tertiary phosphine metal salt ligands.Therefore, hydroformylation process of the present invention can carry out under any excess of desirable free ligand, and for example, every mole the 8th group 4 transition metal needs 1 mole of free list sulfonation tertiary phosphine metal salt ligands at least in the reaction medium.General every mole of the 8th group 4 transition metal (for example rhodium) that is present in the reaction medium adds about 2～300 moles, and preferably about 5～200 moles free ligand suits to most applications, particularly to the catalytic hydroformylation process of rhodium.Certainly, if needed, can in the aldehyde reaction medium, supply with single sulfonation tertiary phosphine metal salt ligands of replenishing in any suitable manner at any time, so that free part maintains predeterminated level in the reaction medium.

The reaction conditions that carries out hydroformylation process of the present invention can be the conventional in the past condition that adopts, and temperature of reaction can be about 1～10 for about 45～200 ℃ and pressure range, 000Psia(pound/inch ²).

Certainly, also to know, though for reaching the optimization of best result and the required reaction conditions of efficient, depend on the experience of people in using the invention of this hydroformylation process, but only need a certain experiment to estimate the optimum operation condition that ensures under the stable condition, this should not can exceed present technique field personnel's ken, and just is easy to obtain by means of reference the present invention more excellent condition as described herein and/or by simple routine experimentation.

For example, in the hydroformylation process of the present invention, the total gas pressure of hydrogen, carbon monoxide and unsaturated olefin initial compounds can be between about 1～10, between the 000Psia.But wishing more in the process of hydroformylation being produced aldehyde that process will be lower than under about 1500Psia at the total gas pressure of hydrogen, carbon monoxide and unsaturated olefin initial compounds carries out, and is preferably lower than about 500Psia.The minimum total pressure of reactant is not strict especially, mainly only depends on that desire obtains the amount of the needed reactant of certain speed of response.More particularly, carbon monoxide pressure of tension is wished at about 1～120Psia in the hydroformylation process of the present invention, and preferably at about 3～90Psia, and the hydrogen dividing potential drop is wished at about 10～160Psia, preferably at about 20～100Psia.The mol ratio H of general gas phase hydrogen and carbon monoxide ₂: CO can be between about 1: 10～100: 1 or is higher again, and better the mol ratio of hydrogen and carbon monoxide is about 1: 1～10: 1.

And as mentioned above, hydroformylation process of the present invention can carry out under about 45～200 ℃ of temperature of reaction.The desired response temperature depends on the concrete used olefin feedstock and the efficient of metal catalyst and expectation certainly in the given method.Generally, wish that the temperature of reaction that adopts is about 60～130 ℃ in rhodium-catalytic hydroformylation process.

At last, the aldehyde product of hydroformylation process of the present invention has purposes widely, and this has known for people and the document record is arranged in prior art, and for example, they are specially adapted to as the raw material of producing pure and mild acid.

As previously mentioned, use the favorable factor of single sulfonation tertiary phosphine metal salt ligands of the present invention a lot, wherein important is that working range is wide, and people can select the most useful appropriate condition combination with the concrete outcome or the requirement that obtain or the most approaching at least hope reaches.For example, single sulfonation tertiary phosphine metal salt ligands can be as the phosphorus part in non-water rhodium process for catalytic hydroformylation, the purpose of this method is with reaching complete acceptable catalytic activity speed under the general desired low hydroformylation pressure and/or under the low rhodium concentration, produces aldehydes and the efficient of sacrifice process within reason and/or the stability of catalyzer from lower molecular weight and high molecular weight olefin.And the volatility of single sulfonation tertiary phosphine metal salt ligands of the present invention is low, and (this salt is in fact non-volatile, promptly, usually before volatilization, just decomposed) make their suit to be used for reducing loss of part and/or catalyzer especially, this being lost in uses general high-volatile phosphorus part to separate by high molecular weight olefin (as C ₆-C ₂₀(using distillation method) can run into during the aldehyde product of the low volatility that carbon atom) obtains.In addition, find a kind of suitable part, the single sulfonation tertiary phosphine metal salt ligands among the present invention for example, it can provide a kind of metal-phosphorus complex catalyzer to the hydroformylation of high molecular weight olefin again to low molecular weight olefins, obviously, this can reduce to minimum to the stock problem of part and/or catalyzer, and even may needs with suitability for industrialized production by from low molecular weight olefins (as C ₂-C ₅Alkene) production lower molecular weight aldehydes changes into from high molecular weight olefin (as C ₆-C ₂₀Alkene) production high molecular weight aldehyde time-like, all complete unnecessary replacing part and/or catalyzer.And non-water hydroformylation process of the present invention can easily adapt to the equipment and the device of existing non-water hydroformylation through transformation, do not need the latter is carried out material alteration.Be surprised to find that also the ratio of just (directly) chain of hydroformylation process of the present invention and different (propping up) chain aldehyde product can change in the wide range inner control by the method that changes metal in this type of part cation group.

Following Example is an illustrative examples of the present invention, is not restrictive.Need to prove that said umber, per-cent and ratio are all represented with weight in embodiment and the claims, unless add explanation in addition.

In following example, use Texanol

The time, it just illustrates effect after the special organic solubilized agent that adds lower concentration in the reaction medium as a kind of thinner easily, it measures speed of response and isomate ratio in the short-term reaction as a kind of medium easily again.So also select Texanol for use

As above-mentioned thinner and medium is because it is a kind of isobutyric aldehyde trimer, therefore as a typical case of the high boiling point aldehyde condensation by-product that generates in long-time continuous circulation hydroformylation process.Be surprised to find that Texanol

Also can be used as single sulfonated triphenylphosphine lithium salts among embodiment 1 and the embodiment 3 with embodiment 2 and embodiment 12 in contain the organic solvent of the phosphine sodium salt of single sulfonation cyclohexyl.

Embodiment 1

The mother solution that has prepared a series of various using rhodium complex catalysts, they mainly contain the reaction product of the solubilising of dicarbonyl rhodium acetylacetonate and various single sulfonated triphenylphosphine metal salt ligands, and they are used for following method the propylene hydroformylation being produced C ₄Aldehydes.

Dicarbonyl rhodium acetylacetonate is at room temperature mixed mutually with the various triphenylphosphine list metal organic sulfonate parts that following chemical formula is arranged:

Wherein M represents a kind of metal shown in the following table 1, and n represents the corresponding integer of positive valence state with used metal, Texanol

Carbowax with different amounts

PEG-600 prepares the mother solution of various rhodium catalysts as solubilizing agent, and wherein the content of rhodium and part is following table 1.

Then the mother solution of the various rhodium catalysts that make like this is used for carrying out the hydroformylation of propylene in the stainless steel autoclave of a magnetic agitation and volume 100mL, this still is connected on the gas piping feeds gas and make and meet the requirements of dividing potential drop in the still.Master gauge assaying reaction pressure also is housed on the autoclave, is accurate to ± 0.1 pound/inch ², platinum-resistance thermometer assaying reaction device solution temperature also is housed, accurately to ± 0.10 ℃.Reactor with two 300 watts of heating collars from indirect heating.The temperature of reactor solution is controlled with platinum sensor, and transmitter is received the temperature of the ratio temperature regulator control externally heating circle of outside.

In each non-water aldehyde reaction, with the about 14g of about 15mL() the rhodium catalyst mother solution that makes by last method joins in the reactor under the nitrogen atmosphere, is heated to used temperature of reaction (tabulating 1 as follows).Then reactor pressure is discharged into 5Psia, will be pre-mixed 1: 1: 1 carbon monoxide of thing again: hydrogen: the propylene mixed gas is added reactor (dividing potential drop sees Table 1) by gas piping, so aldehyde reaction just takes place propylene.

In the routine operating pressure scope of reactor, the reactor pressure 5Psia that whenever falls progressively measures the speed of wherein aldehyde reaction, and the latter is with the C of every liter of generation per hour ₄The mole number of aldehydes calculates, and also uses the mol ratio of a gas chromatography determination straight chain formula (butyraldehyde-n) and chain type (2 methyl propanal) product simultaneously, the results are shown in following table 1.

Embodiment 2

The complex compound catalyst mother solution of rhodium is pressed the listed aldehyde reaction condition of following table 2, repeat to be used for from dicarbapentaborane methyl ethyl diketone, Texanol among the embodiment 1 Prepare the rhodium catalyst parent with single sulfonation tertiary phosphine metal-salt, and carry out identical program of propylene hydroformylation and condition.Single sulfonation tertiary phosphine metal salt ligands of using in the experiment 1 is single sulfonation cyclohexyl diphenylphosphine sodium salt part (CHDPPMS-Na), and it has chemical formula

And test the part of using in 2 is single sulfonation dicyclohexyl Phenylphosphine sodium salt part (DCHPPMS-Na), has chemical formula

Generate C with every liter per hour ₄The ratio of aldehyde reaction speed that the mole number of aldehydes is represented and straight chain (butyraldehyde-n) and side chain (2 methyl propanal) product the results are shown in table 2 all by measuring like that among the embodiment 1.

Embodiment 3

Carry out the continuous hydroformylation of butene-1 with single sulfonated triphenylphosphine metal salt ligands with following method.

Non-water hydroformylation is carried out in glass reactor, and operation is undertaken by continuous once-through butene-1 hydroformylation mode.Reactor is 3 ounce pressure bottles that are immersed in the oil bath, and the front is equipped with and is looked glass port.System with nitrogen purging after, with a syringe about 20 milliliters of freshly prepd rhodium catalyst mother solution in reactor.Mother solution contains the 200PPm that has an appointment with the rhodium that the form of dicarbonyl rhodium acetylacetonate adds, and is equivalent to the structural formula that every mole of rhodium closes about 118 molar equivalents be

Single sulfonated triphenylphosphine lithium salts part and Texanol After the reactor sealing, wash system with nitrogen again, again oil bath is heated to meet the requirements of the aldehyde reaction temperature.Aldehyde reaction is to carry out under the total gas pressure of about 160Psig, and following table 3 has been listed the dividing potential drop of hydrogen, carbon monoxide and butene-1, and all the other pressure are nitrogen and aldehyde product.

With mass flowmeter control, unstripped gas is distributed in the mother solution by pore stainless steel sparger the flow of various unstripped gass (carbon monoxide, hydrogen, butene-1 and nitrogen) respectively.Temperature of reaction is listed in following table 3.Unreacted that part of unstripped gas and C ₅The aldehyde product is overflowed together, exit gas is analyzed in during about 12 days of operate continuously.C with every liter per hour ₅Approximate per day speed of response that the mole number of aldehyde product is represented and straight chain (valeraldehyde) are listed in following table 3 with the ratio of side chain (2 methyl butyraldehyde) product.

Embodiment 4

Catalyst precursor solutions is carried out continuous hydroformylation according to the method identical with embodiment 3 to butene-1, and this mother solution contains the about 200PPm rhodium that adds with the dicarbonyl rhodium acetylacetonate form, about 10: the Texanol 1(weight ratio)

And Carbowax

The mixture of PEG-600 (about 8.5% weight) is as solubilizing agent, is equivalent to the chemical formula that every mole of rhodium closes about 118 molar equivalents in addition be

Single sulfonated triphenylphosphine sodium salt part, reaction conditions is seen following table 4.

Following table 4 has been listed the roughly composition of catalyzer and with every liter per hour C ₅The per day speed of response that the mole number of aldehyde product is represented, and the ratio of straight chain (valeraldehyde) and side chain (2 methyl butyraldehyde) product.

Embodiment 5

Carry out the continuous hydroformylation of butene-1 with catalyst precursor solutions according to the method identical with embodiment 3, this mother solution contains the about 200PPm rhodium, about 20 that adds with the dicarbonyl rhodium acetylacetonate form: the Texanol 1(weight ratio) And Carbowax The mixture of PEG-600 (about 4.3%(weight)) making solubilizing agent also contains and is equivalent to the chemical formula that every mole of rhodium closes about 118 molar equivalents and is

Single sulfonated triphenylphosphine calcium salt part, reaction conditions is seen following table 5.

Following table 5 has been listed the roughly composition of catalyzer and with every liter per hour C ₅The per day speed of response that the mole number of aldehyde product is represented also has the ratio of straight chain (just-valeral) and side chain (2 methyl butyraldehyde) product.

Embodiment 6

Using following method, is olefin feedstock successive catalyst liquid echo plex mode with the octene-1, has carried out 6 days aldehyde reaction.

Used liquid returning reactor system, comprise 2.8 liters of stainless steel stirred-tank reactors of two polyphones, each reactor have a vertically arranged agitator and one be contained near reactor bottom in order to feed the round tubular sparger of synthesis gas.A lot of holes are arranged on the sparger, and its size can be enough to the air-flow of needs is added liquid phase.Reactor 1 has a silicone oil shell, is used to make the material temperature in the reactor to rise to temperature of reaction, and the reaction soln in the reactor 2 then heats with electricradiator.These two reactors all are provided with the inside spiral coil cooling tube that control reaction temperature is used.There is pipeline to connect between the reactor 1 and 2, so that all unreacted gases are transported to reactor 2 from reactor 1, also be provided with pipeline in addition and connect two reactors so that with pump the reaction soln that part contains aldehyde product and catalyzer is delivered to reactor 2 from reactor 1, unreacted alkene can be carried out hydroformylation again at reactor 2 in the reactor 1.

Each reactor also has a pneumatic liquid-level controller so that the automatic control of liquid level in the realization response device.Reactor also has one to inject the pipeline of liquefied olefines and one for volume pump and send into the pipeline of synthesis gas by sparger in addition, and replenish synthesis gas be by with carry same line of pipes of unreacted synthesis gas body and function to be added to reactor 2 from reactor 1.Reactor 2 also is provided with a venting port, in order to get rid of unreacted gas.Partial reaction solution with a pipeline reactor 2 bottoms linked to each other with the vaporizer top, so that can be delivered to vaporizer from reactor 2 with pump.Keep low pressure in the vaporizer with vacuum pump.The aldehyde that is evaporated has broken away from the non-volatilization component in the reaction soln at the solution-air segregation section of vaporizer.Remainder contains the reaction soln of non-volatile catalyzer by return line pumped back reactor 1.Also be provided with pneumatic liquid-level controller on the return line.The aldehyde product that steams is collected after the liquefaction in the product susceptor by a water cooled condenser.

The carrying out of aldehyde reaction, be in reactor 1, to add about 1.00L(893g) catalyst precursor solutions, wherein contain dicarbonyl rhodium acetylacetonate (about 600PPm rhodium), contain about 16%(weight again) the 3-(diphenylphosphino that following chemical formula is arranged)-Phenylsulfonic acid sodium salt part

(every mole of rhodium is roughly equal to the part of 80 molar equivalents greatly), also contain about 10%(weight as solubilizing agent) methyl alcohol, about 30%(weight) TERGLTOL 24-L-75N and CARBOWAX

The mixture of TPEG 990 (weight ratio is 4: 1) and about 45%(weight) C ₉Aldehyde.

In reactor 2, add about 1.00 liters (897 grams) with a kind of catalyst precursor solutions.Reactor assembly to drive the oxygen of no longer holding the post and how to exist, is heated to reactor the temperature that following table 6 is listed with the nitrogen purge again then.Hydrogen that purifying is crossed and carbon monoxide air-flow controlledly are added to reactor 1 bottom by sparger, reactor pressure are increased to the working pressure that following table 6 provides again.Liquid level in the reactor 1 is owing to the pumping liquid octene-1 and be converted into the liquid aldehydes product and begin to rise, and at this moment the partially liq reaction soln in the reactor 1 is got to the top of reactor 2 by-pipeline to be enough to keep liquid level constant speed in the reaction 1 with pump.Pressure in the reactor 2 is brought up to the working pressure that following table 6 provides.Analyze and measure the gas of emitting by reactor 2.With synthesis gas (CO and the H that adds ₂) controlledly be added to reactor 2, keep in the reactor 2 they desired dividing potential drops.In whole hydroformylation process, all to keep temperature of reaction and pressure.Because the liquid level in the reactor 2 is owing to the generation from reactor 1 pumping liquid and liquid aldehydes product begins to rise, liquid level keeps constant speed to pump into evaporation/separator in the reactor 2 to be enough to make with a part of liquid reaction solution.Thick aldehyde product is separated from liquid reaction solution under 155 ℃ and about 40mmHg pressure, and condensation is also collected in the product susceptor.The remaining liquid reaction solution that contains non-volatile catalyzer turns back to reactor 1.Add methyl alcohol with one Tai Mierdun-Roy (Milton-Roy) micropump continuously to reactor 1, replenish the methyl alcohol that exists in the initial catalyst component.At last two days of test, add Virahol and replace methyl alcohol.Methyl alcohol and Virahol and aldehyde C-9 product generation partial reaction generate dicarbaldehyde acetal and diisopropyl acetal respectively, generate the latter's somewhat lesser degree.These byproducts are also reinstated method of evaporation with main reaction product one and are taken out continuously.

The hydroformylation of above-mentioned octene-1 has been carried out 6 days continuously.

Following table 6 has been listed the condition of aldehyde reaction, and the C that represents with the mole number of every liter per hour ₉The speed that aldehydes generates also has the ratio of linear chain aldehyde and branched chain aldehyde product, and promptly aldehyde C-9 compares 2 methyl octylaldehyde.

High performance liquid phase bag spectrum has illustrated that to the routine analysis of aldehyde reaction medium in two reactors ligand concentration does not have significant change 6 days operating period in the above-mentioned medium.

Embodiment 7

Use catalyst precursor solutions to carry out the continuous hydroformylation of butene-1, contain the about 200PPm rhodium that adds with dicarbapentaborane methyl ethyl diketone form in this mother solution, contain again and have an appointment 7: the Texanol 1(weight ratio) according to method similarly to Example 3

And Carbowax

The mixture of PEG-600 (about 10.9%(weight)), also contains the chemical formula that every mole of rhodium is roughly equal to 118 molar equivalents and be as solubilizing agent

Single sulfonated triphenylphosphine barium salt part, reaction conditions is seen following table 7.

Following table 7 has been listed the roughly composition of catalyzer and with every liter per hour C ₅The per day speed of response that the mole number of aldehyde product is represented, the ratio of straight chain (valeraldehyde) and side chain (2 methyl butyraldehyde) product in addition.

Embodiment 8

According to carrying out the continuous hydroformylation of propylene with catalyst precursor solutions with embodiment 3 same methods, this mother solution contains the about 200PPm rhodium that adds with the dicarbonyl rhodium acetylacetonate form, contain again and have an appointment 8: the mixture of the Texanol 1(weight ratio) and Carbowax PEG-600 (about 10.0%(weight)) as solubilizing agent, also containing and being equivalent to the chemical formula that every mole of rhodium is roughly equal to 118 molar equivalents is triphenylphosphine rubidium salt part

Single sulfonated triphenylphosphine rubidium salt part, reaction conditions is seen following table 8.

Following table 8 has been listed the roughly composition of catalyzer and with every liter per hour products C ₄The per day speed of response that aldehydes is represented, the ratio of straight chain (butyraldehyde-n) and side chain (2 methyl propanal) product in addition.

Embodiment 9

To chemical formula be

The solubleness of various single sulfonated triphenylphosphine metal salt ligands in different aldehyde measure, metal shown in the table 9 below the M representative in the formula, n represents the integer of the positive valence state of used metal, and measuring method is that to increase various solid metal salt parts gradually in the various aldehydes that keep constant temperature and stir saturated until solution.This test the results are shown in following table 9.

Embodiment 10

By 1.5g(1: 4 weight ratios) CARBOWAX

TPEG-900 and TERGITOL The part solubilizing agent additive that the mixture of NP-9 is formed exists down, has measured chemical formula and has been

The solubleness of various single sulfonated triphenylphosphine metal salt ligands in aldehyde C-9, the listed metal of table 10 below the M representative in the formula, n represents the integer of the positive valence state of used metal.The measuring method of solubleness is that can the solubleness of salt part in above-mentioned solubilizing agent mixture of measuring 100 ℃ of mensuration differences add 3 gram aldehyde C-9s then earlier, observe at room temperature keep a homogeneous phase solution.The calculated value of the various part weight percent solubleness of calculating is listed in following table 10.

Embodiment 11

Complex catalyst mother solution and aldehyde reaction condition with the listed various rhodiums of following table 11, repeat the preparation various rhodium catalyst parents identical and carry out the used method and the condition of hydroformylation of propylene, when preparing mother solution be with dicarbonyl rhodium acetylacetonate, a kind of chemical formula with embodiment 1

Single sulfonated triphenylphosphine sodium salt part, also used about 3.5: the Texanol 1(weight ratio)

With about 20%(weight) mixture or mixed solubilizers as the solubilizing agent additive of table 11 listed (giving the weight ratio of this solubilizing agent mixture).Embodiment 1 has measured like that by every liter per hour and has generated C ₄The mol ratio of aldehyde reaction speed that the mole number of aldehydes is represented and straight chain (butyraldehyde-n) and side chain (2 methyl propanal) product the results are shown in following table 11.

Embodiment 12

With a kind of catalyst precursor solutions according to similarly to Example 3 method, butene-1 is carried out continuous hydroformylation, this mother solution contains about 200PPm rhodium, the Texanol that adds with the dicarbonyl rhodium acetylacetonate form, also contains and is equivalent to a kind of single sulfonation dicyclohexyl Phenylphosphine sodium salt part with following chemical formula that every mole of rhodium is roughly equal to 14 molar equivalents

Reaction conditions is face table 12 as follows.

Below table 12 listed the roughly composition of catalyzer, with every liter per hour products C ₅Per day speed of response that aldehydes is represented and straight chain (just-valeral) are to the ratio of side chain (2 methyl butyraldehyde) product.

Embodiment 13

Repeat the preparation rhodium catalyst mother solution identical and carry out the used method and the condition of hydroformylation of laurylene-1 with the complex compound catalyst mother solution of the listed various rhodiums of following table 13 and various aldehyde reaction conditions with embodiment 1; Use dicarbonyl rhodium acetylacetonate, a kind of about 9 during the preparation mother solution: the mixture of the TEXANOL 1(weight ratio) and CARBOWAX TPEG-990 (about 10.0%(weight)), also used chemical formula to be as solubilizing agent

Single sulfonated triphenylphosphine sodium salt part.Also measured the C that generates with every liter per hour like that according to embodiment 1 ₁₃The aldehyde reaction speed that the mole number of aldehydes is represented, and the mol ratio of straight chain (positive tridecyl aldehyde) and side chain (2-methyl lauric aldehyde) product the results are shown in following table 13.

Embodiment 14

, repeat the preparation various rhodium catalyst mother solution identical and carry out used method of hydroformylation and condition as the reaction conditions in hydroformylation raw material and the table with the listed various alpha-olefins of the complex catalyst mother solution of rhodium and following table 14 with embodiment 1; Use dicarbonyl rhodium acetylacetonate, a kind of about 3 during the preparation mother solution: the Texanol 1(weight ratio)

And CARBOWax

The about 25%(weight of TPEG-990()) mixture has also used a kind of chemical formula to be as solubilizing agent

Single sulfonated triphenylphosphine sodium salt part.Measured the aldehyde reaction speed of representing with the mole number of every liter per hour generation aldehydes according to embodiment 1 again, and the mol ratio of linear chain aldehyde and branched chain aldehyde product, the results are shown in following table 14.

Embodiment 15

With following table 15 listed various using rhodium complex catalysts mother solution and reaction conditions, repeat the preparation various rhodium catalyst mother solution identical and carry out used method of octene-1 hydroformylation and condition with embodiment 1; Use dicarbonyl rhodium acetylacetonate, a kind of chemical formula to be during the preparation mother solution

Single sulfonated triphenylphosphine sodium salt part, also used Texanol and different amounts (the about 15%(weight of experiment 1 usefulness), test the about 10%(weight of 2～5 usefulness)) the various mixtures of different types of solubilizing agent additive (face table 15 as follows).Measured like that with every liter per hour according to embodiment 1 again and generated C ₉The aldehyde reaction speed that the mole number of aldehydes is represented, and the mol ratio of straight chain (n-nonyl aldehyde) and side chain (2 methyl octylaldehyde) product the results are shown in following table 15.

Embodiment 16

The various solubilizing agent additives of part and various mixture thereof in the presence of, measure chemical formula and be

Single sulfonated triphenylphosphine sodium salt part (TPPMS-Na) at C ₉Solubleness in the aldehyde (aldehyde C-9).Solubleness survey method is, under 100 ℃ solid TPPMS-Na part is dissolved in solubilizing agent or their mixture, adds aldehyde C-9 then, observes whether keep homogeneous phase solution under 100 ℃ and room temperature.Used solubilizing agent and composition thereof is 1: 2 with the weight ratio of aldehyde C-9.The results are shown in the following table 16.

The solubleness of single sulfonated triphenylphosphine sodium salt part (TPPMS-Na) in various aldehyde measure, method be with solid TPPMS-Na part 100 ℃ be dissolved in TERGITOL 24-L-75N/CARBOWAX TPEG-900(4: in the mixed solubilizers 1 weight ratio), add aldehyde then, observe under the room temperature and can remain homogeneous phase solution.The weight ratio of used mixed solubilizers and various aldehydes is 1: 2.The results are shown in following table 17.

Embodiment 18

With listed various using rhodium complex catalysts mother solution of following table 18 and aldehyde reaction condition, repeat the preparation a kind of rhodium catalyst mother solution identical and carry out the used method and the condition of hydroformylation of laurylene-1 with embodiment 1; Preparation with the various single sulfonated triphenylphosphine metal salt ligands shown in dicarbonyl rhodium acetylacetonate, the following table 18, has also used about 3.5 for coordination: the enanthaldehyde 1(weight ratio) and about 20%(weight during mother solution) the solubilizing agent additive or with the mixture of the mixed solubilizers (wherein also having provided the part by weight of this mixed solubilizers) shown in institute's following table 18.Measured the aldehyde reaction speed of representing with the mole number of every liter per hour generation aldehydes according to embodiment 1 again, and the mol ratio of straight chain (positive tridecyl aldehyde) and side chain (2-methyl lauric aldehyde) product, the results are shown in following table 18.

Embodiment 19

Measure by the following method and compared single sulfonated triphenylphosphine sodium salt part and promote catalytic water and the catalytic activity of non-aqueous solution in the alhpa olefin hydroformylation process of various molecular weight.

With following table 19 listed various rhodium complex mother solution and aldehyde reaction condition, repeat 1 identical preparing the rhodium catalyst mother solution and carry out various alpha-olefin hydroformylations used method and condition with embodiment; Preparation uses dicarbonyl rhodium acetylacetonate during mother solution, also used, chemical formula is present in single sulfonated triphenylphosphine sodium salt (shown in following table 19) in non-water organic solubilized agent solution or the water shown in embodiment 4.Water and nonaqueous phase aldehyde reaction all are to carry out under all identical situations of conditions such as the dividing potential drop of concentration, hydrogen and the carbon monoxide of temperature, rhodium and part and concentration of olefin.Measured the aldehyde reaction speed of representing with the mole number of every liter per hour generation aldehydes like that according to embodiment 1 again, and the mol ratio of straight chain and branched chain aldehyde product, the results are shown in following table 19.

The present invention has multiple improvement and mutation, and this is obviously for those skilled in the art, self-evidently is, this class is improved and mutation all will be included within the spirit and scope of the scope of present patent application and claims.

Table 20

Trade(brand)name R ⁶X

TERGITOL 25-L-5 C ₁₂-C ^a ₁₅5

TERGITOL 26-L-5 C ₁₂-C ^a ₁₆5

TERGITOL

15-S-3 C ₁₁-C ^b ₁₅3

TERGITOL

15-S-7 C ₁₁-C ^b ₁₅7

TERGITOL

NP-4 nonyl phenyl ^c4

TERGITOL

NP-9 nonyl phenyl ^c9

TERGITOL

24-L-15N C ₁₂-C ^a ₁₄4.8

TERGITOL

24-L-50N C ₁₂-C ^a ₁₄6.5

TERGITOL

24-L-75N C ₁₂-C ^a ₁₄8.0

A) straight chain-primary alkyl

B) straight chain-secondary alkyl

C) side chain nonyl

Table 1

Experiment part Texanol / weight % speed of response straight chain/

Numbering M+=Carbowax

Carbowax

Mole/branched chain aldehyde

The mole of PEG 600 PEG 600 Lhr

The weight ratio ratio

1 Li ⁺100∶0 ^d0 0.35 ^a6.3

2 Na ⁺10∶1 8.5 0.28 ^b，c6.4

3 K ⁺9∶1 8.7 0.87 ^a5.1

4 Rb ⁺8∶1 10.0 0.70 ^a5.6

5 Cs ⁺Speed reduced in 7: 1 10.85 ^{A, e}

6 Ca ⁺⁺20∶1 4.3 0.51 ^a4.7

7 Ba ⁺⁺7∶1 10.9 1.43 ^a4.1

8 Sr ⁺⁺18: 1 4.45 no speed ^{A, e}-

A, condition: 200PPm Rh; Every mole of rhodium closes joining of about 120 molar equivalents

Table 3

Experimental result-daily mean

The speed straight chain/

The service temperature rhodium ^*Rubbing of part dividing potential drop (psia) mole/chain aldehyde

Fate ℃ ppm weight % CO H ₂C ₄H ₈You compare L/Hr

0.8 101. 198. 7.9 18. 48. 19 1.02 30.34

4.0 101. 258. 10.3 17. 52. 49 1.25 11.20

4.8 101. 249. 9.9 17. 52. 50 1.19 -

6.0 101. 242. 9.7 17. 52 50 1.27 2.98

6.9 101. 244. 9.8 19. 50. 41 1.28 31.75

8.0 102. 250. 10.0 18. 56. 38 1.28 40.30

9.0 102. 252. 10.1 18. 57. 38 1.30 28.90

10.0 102. 249. 10.0 18. 57. 38 1.27 29.63

10.7 102. 247. 9.9 18. 57. 38 1.27 37.18

11.6 103. 245. 9.8 18. 57. 38 1.21 30.18

* numerical value change has reflected reactor solution liquid level variation every day.

Embodiment 4

Table 4

Test-results-daily mean

The speed straight chain/

The service temperature rhodium ^*Part ^*Rubbing of dividing potential drop (psia) mole/chain aldehyde

Fate ℃ ppm weight % CO H ₂C ₄H ₈L/H _rYou compare

0.9 102 197 5.9 51. 59. 20. 1.68 7.68

2.0 101 206 6.2 51. 47. 22. 1.81 9.21

3.0 101 220 6.6 20. 53. 24. 1.60 21.08

4.0 101 226 6.8 20. 30. 39. 2.50 19.83

5.9 101 224 6.7 15. 63. 31. 2.06 22.82

5.6 101 223 6.7 15. 64. 31. 2.05 23.74

^*Numerical value change has reflected reactor solution liquid level variation every day.

Table 5

Test-results-daily mean

Dividing potential drop speed straight chain/

The service temperature rhodium ^*Part ^*(psia) mole/chain aldehyde rubs

Fate ℃ ppm weight % CO H ₂C ₄H ₈You compare L/Hr

0.9 101 179 3.9 20. 59. 20. 1.27 12.84

1.7 101 178 3.9 19. 55. 18. 1.38 14.44

5.0 101 213 4.7 16. 47. 36. 1.62 13.06

5.9 101 222 4.9 17. 51. 29. 1.64 17.67

7.0 101 220 4.8 13. 43. 50. 1.85 20.95

8.0 101 235 5.2 17. 41. 36. 2.09 18.76

9.0 102 245 5.4 17. 36. 52. 2.19 18.38

10.0 102 261 5.7 18. 30. 56. 1.40 20.52

11.9 102 287 6.3 17. 29. 59. 1.62 21.86

11.8 102 317 7.0 17. 29. 63. 1.51 18.90

12.6 103 128 7.2 18. 29. 61. 1.83 28.03

Table 6

Operation fate 1236

The octene-1 raw material, the %(mole)

Octene-1 98.28 98.28 98.28 98.28

Octene-2 1.54 1.54 1.54 1.54

Octane 0.17 0.17 0.17 0.17

Reactor 1

Temperature 80.1 80.0 80.1 80.0

Pressure, psia 65.2 65.2 65.2 64.7

H ₂，psia 47.6 56.9 56.6 50.7

CO，psia 17.0 7.8 8.1 10.1

Octene-1 %(mole) 24.4 22.3 22.8 20.2

Octene-2%(mole) 5.2 5.4 5.4 4.6

Reactor 2

Temperature 85.8 85.6 85.7 85.0

Pressure, psia 51.7 50.7 51.7 50.7

H ₂，psia 40.1 48.1 44.7 39.7

CO，psia 9.9 2.2 6.5 8.3

Octene-1 %(mole) 10.8 8.6 7.0 5.3

Octene-2%(mole) 5.4 7.2 6.2 5.6

The result

C ₉Aldehydes/mole/L/hr 1.02 0.84 0.81 1.02

The ratio 14.0 27.2 24.7 22.5 of straight chain/branched chain aldehyde

Table 7

The service temperature rhodium ^*Part ^*Dividing potential drop speed straight chain/side chain

(psia) mole/

Fate ℃ ppm weight % CO H ₂C ₄H ₈The mol ratio of L/Hr aldehyde

1.0 101. 186. 5.1 18. 70. 11. 2.07 6.91

1.8 101. 183. 5.0 16. 62. 14. 2.10 7.10

5.0 101. 183. 5.0 12. 66. 19. 2.51 7.12

5.9 101. 203. 5.6 13. 66. 20. 2.52 7.03

6.9 101. 195. 5.4 14. 62. 22. 2.71 6.32

7.9 101. 187. 5.1 16. 55. 24. 2.71 6.16

9.0 102. 200. 5.5 18. 60. 23. 2.73 6.01

7.0 102. 207. 5.7 18. 62. 22. 2.60 6.02

11.0 102. 220. 6.1 19. 63. 21. 2.46 6.20

11.7 102. 234. 6.4 20. 63. 21. 2.37 6.14

12.6 103. 240. 6.6 20. 63. 22. 2.30 5.85

^*Numerical value change has reflected reactor solution liquid level variation every day

Table 8

The speed straight chain/

The service temperature rhodium ^*Part ^*Rubbing of dividing potential drop mole/chain aldehyde

Fate ℃ ppm weight % CO H ₂C ₃H ₆You compare L/Hr

1.0 99. 244. 7.3 33. 53. 17. 1.01 5.15

2.0 106. 272. 8.2 28. 54. 18. 1.24 6.19

3.0 102. 182. 5.5 23. 55. 19. 0.68 5.86

4.0 102. 189. 5.7 23. 55. 19. 0.58 6.04

4.9 104. 202. 6.1 23. 55. 19. 0.58 6.12

5.8 103. 216. 6.5 23 55. 20. 0.58 6.45

6.7 98. 222. 6.7 24. 56. 20. 0.41 6.60

Table 9

Metal-salt solubleness, %(weight)

Wherein M representative

Aldehyde temperature ℃ Li ⁺Na ⁺Rb ⁺Ba ⁺⁺

Propionic aldehyde 35 8.8 16.3 6.6 0.5

Butyraldehyde 60 0.5 10.0 1.4 0.6

Valeral 80＜0.5 5.3 3.3 0.1

Enanthaldehyde 80＜0.7 0.4 3.8 0.2

Aldehyde C-9 80＜0.5 0.5 0.9 0.2

Tridecyl aldehyde 80＜0.5 0.5 0.5 0.3

Table 10

%(weight)

Metal-salt solubleness

M＝ 25℃

Li ⁺12

Na ⁺25

Rb ⁺25

Cs ⁺＞10

Ca ⁺⁺18

Ba ⁺⁺33

Table 11

Experiment speed of response straight chain/side chain

Added solubilizing agent

The mol ratio of numbering mole/L/hr aldehyde

1 TERGITOL

NP-9 0.67 5.1

2 TERGITOL

15-S-7 0.49 4.7

3 TERGITOL

24-L-75N/NIAX 0.54 5.3

PPG 1025（4∶1）

4 TERGITOL

NP-4/CARBOWAX 0.59 6.0

TPEG 990（4∶1）

5 TERGITOL 15-S-3/CARBOWAX 0.25 5.6

PEG 600/ dimethyl sulfoxide (DMSO)

（4∶1∶1）

6 TERGITOL 15-S-7/CARBOWAX 0.75 5.0

TPEG 990/N-methyl-2-pyrrolidone

（4∶1∶1）

Reaction conditions: 100 ℃; The 200PPm rhodium; Every mole of rhodium is roughly equal to the part (rhodium be equivalent to part weight 8.3%) of 120 molar equivalents; 90Psia1: 1: 1H ₂: CO: C ₃H ₆

Table 12

Test-results-daily mean

Dividing potential drop speed straight chain/

The service temperature rhodium ^*Part ^*(psia) mole/chain aldehyde rubs

Fate ℃ ppm weight % CO H ₂C ₄H ₈You compare L/Hr

0.8 80 172 0.8 40 39 3 0.86 1.86

1.9 80 168 0.8 38 41 4 1.02 1.88

2.8 80 182 0.8 39 41 3 0.87 1.99

3.9 80 186 0.8 38 42 4 0.85 1.84

5.0 80 191 0.9 38 42 4 0.88 1.83

5.8 80 195 0.9 38 42 5 0.86 1.79

6.8 80 200 0.9 38 43 4 0.80 1.95

7.8 80 249 1.1 38 44 5 0.86 1.78

9.0 80 257 1.2 39 43 5 0.72 1.75

10.0 80 272 1.2 42 38 6 0.94 1.79

10.9 80 274 1.2 41 39 6 0.95 1.89

11.0 80 274 1.2 41 39 6 0.99 1.92

12.9 80 299 1.3 41 39 5 0.95 1.77

^*Numerical value change has reflected liquid level variation in reactor solution every day.

Table 13

Straight chain/

The experiment rhodium ^*Rubbing of temperature part/rhodium dividing potential drop laurylene-1 speed of response chain aldehyde

Numbering mol ratio H ₂CO mole/that ratio

ppm ℃ psia psia ml L/Hr

1 25 100 10 20 40 5.0 1.37 3.4

2 200 120 200 20 40 5.0 1.24 9.56

3 500 70 50 20 40 5.0 0.51 5.5

4 200 100 100 10 40 5.0 1.13 16.9

5 200 100 100 100 40 5.0 1.41 4.1

Rh ^*=rhodium

Table 14

Experiment numbers alpha-olefin speed of response straight chain/branched chain aldehyde

Mole/L/hr mol ratio

1 propylene ^a1.72 5.0

2 butene-1s ^b5.96 12.8

3 hexenes-1 ^b5.21 13.4

4 octene-1s ^b4.17 14.8

5 laurylenes-1 ^b1.04 10.8

6 tetradecenes-1 ^b0.65 12.6

Table 15

TEXANOL/

Experiment solubilizing agent speed of response straight chain/side chain

The mol ratio of numbering (weight ratio) mole/L/hr aldehyde

1 Texanol / 0.95 18.7

Dimethyl sulfoxide (DMSO) (5.5: 1)

2 Texanol

/ 0.47 26.6

Benzonitrile (18: 1)

3 Texanol

/ sulfolane 0.98 19.1

（8∶1）

4 Texanol /Carbo- 1.12 17.6

wax PEG 150

5. Texanol

/Niax 0.71 23.9

PPG-1025

Reaction conditions: 90 ℃; The 200PPm rhodium; 10%(weight) part;

Part: rhodium (mol ratio)=137; The 5mL octene-1; 75Psia4: 1 H ₂: Co.

Table 16

The solubleness of TPPMS-Na

(weight percent)

25 ℃ 100 ℃ of solubilizing agent

TERGITOL

NP-4 2 6

TERGITOL

NP-9 4 6

TERGITOL

15-S-3 2 8

TERGITOL

15-S-7 4 8

TERGITOL

24-L-15N 2 8

TERGITOL

24-L-50N 4 8

TERGITOL

24-L-75N 6 8

TERGITOL 25-L-5 4 6

TERGITOL

26-L-5 2 6

CARBCWAX

PEG-600 ＞8a ＞8a

CARBCWAX

TPEG-990 ＞2a ＞2a

NIAX PPG-1025 ＜2 2

Binary system (weight ratio)

TERGITOL

NP-4/CARBCWAX

TPEG 990（4∶1） 8 10

TERGITOL

15-S-7/CARBOWAX

TPEG 990（3∶1） 10 8

TERGITOL

24-L-75N/CARBOWAX

TPEG 990（4∶1） 12 14

TERGITOL

NP-9/CARBOWAX

PEG 600（3∶1） 10 ＞10

TERGITOL 15-S-3/CARBOWAX

PEG 600（4∶1） 2 ＞10

TERGITOL 24-L-50N/CARBOWAX

PEG 600（4∶1）＞10 ＞10

TERGITOL

24-L-75N/NIAX PPG 1025（2∶1）＞10 ＞10

Ternary system (weight ratio)

TERGITOL

24-L-75N/CARBOWAX

TPEG 990/ ＞16 -

Methyl alcohol (4: 1: 1)

TERGITOL

15-S-3/CARSOWAX PEG 600/ ＞6 -

Methyl alcohol (4: 1: 1)

TERGITOL

NP-9/CARBOWAX

-PEG 600/ ＞12 -

Methyl alcohol (3: 1: 1)

A forms two translucent liquid layers.

Table 17

Aldehyde TPPMS-Na is at 25 ℃

The time weight percent solubleness

Butyraldehyde＞20

Valeral＞20

Enanthaldehyde 18

Aldehyde C-9 12

Tridecyl aldehyde 8

Table 18

Straight chain/

Rubbing of experiment speed of response chain aldehyde

The solubilizing agent that numbering phosphine part adds ^eYou compare mole/L/hr

1.TPPMS-Na ^aTERGITOL

NP-9 0.77 14.2

2. ″ CARBOWAX PEG-600 0.72 12.0

3. ″ TERGITOL 24-L-75N/ 0.62 13.6

CARBOWAX

TPEG-990（4∶1）

4. ″ TERGITOL

15-S-3/NIAX PPG-1025/ 0.51 13.2

Dimethyl sulfoxide (DMSO) (4: 1: 1)

5. TPPMS-Ba ^bCARBOWAX

PEG-600 1.22 10.0

6. ″ TERGITOL

24-L-75N/ 0.76 10.9

CARBOWAX TPEG-990（4∶1）

7. ″ TERGITOL

15-S-7/Carbo- 0.45 9.4

wax TPEG-990（3∶1）

8. TPPMS-Rb ^cCARBCWAX

PEG-600 0.69 16.3

9. TPPMS-Li ^dCARBOWAX

PEG-600 0.30 13.7

Reaction conditions: 100 ℃; The 200PPm rhodium; Every mole of rhodium is roughly equal to the part of 120 molar equivalents; 60Psia 2: 1H ₂: Co; 5mL(3.7g) laurylene-1

A) single sulfonated triphenylphosphine sodium salt TPPMS-Na=8.3%(weight) with chemical formula shown in the embodiment 4.

B) single sulfonated triphenylphosphine barium salt TPPMS-Ba=9.3%(weight) with chemical formula shown in the embodiment 7.

C) single sulfonated triphenylphosphine rubidium salt TPPMS-Rb=9.7%(weight) with chemical formula shown in the embodiment 8.

D) single sulfonated triphenylphosphine lithium salts TPPMS-Li=7.9%(weight) with chemical formula shown in the embodiment 3.

E) in the experiment 2,5,6,8 and 9, two liquid organic phases appear in the aldehyde reaction medium; The upper strata water white transparency, lower floor is yellow.But this there is no harmful effect to aldehyde reaction.

Table 19

Non-water aldehyde reaction medium water aldehyde reaction medium

Speed of response straight chain/side reaction speed straight chain/side chain

The mol ratio of the mole/L aldehyde of alkene mole/L chain aldehyde

/ hr that ratio/hr

Propylene 2.60 ^a4.8 0.07 ^c19.3

Butene-1 6.94 ^b5.1 0.44 ^d37.1

Octene-1 2.84 ^b5.8 0.11 ^d40.9

Laurylene-1 4.49 ^b6.6 0.03 ^d43.4

A) reaction conditions: 300PPm rhodium; 8.7%(weight) part (every mole of rhodium closes 80 moles of parts); 2.6: the Texanol 1(weight ratio)

And Carbowax The mixture of TPEG-990 (about 25%(weight)) as solubilizing agent; 100 ℃; 90Psia1: 1: 1 H ₂: Co: propylene.

B) reaction conditions: 300PPm rhodium; 8.7%(weight) part (every mole of rhodium closes 80 moles of parts); 2.6: the Texanol 1(weight ratio)

And Carbowax The mixture of TPEG-990 (about 25%(weight)) as solubilizing agent; 100 ℃; 90Psia1: 1 H ₂: Co, 5 milliliters of corresponding alkene.

C) reaction conditions: 300PPm rhodium; 8.7%(weight) part (every mole of rhodium closes 80 moles of parts); Use water as solvent; 100 ℃; 90Psia1: 1: 1 H ₂: Co: propylene.

D) reaction conditions: 300PPm rhodium; 8.7%(weight) part (every mole of rhodium closes 80 moles of parts); Use water as solvent; 100 ℃; 1: 1 H of 90Psia ₂: Co; 5 milliliters of corresponding alkene.

Claims

1, a kind of non-water hydroformylation process of producing aldehydes, this method comprises makes the alkene unsaturated organic compound that contains 2 to 20 carbon atoms, contain alkene unsaturated organic compound, aldehyde product, by the rhodium of solubilising-phosphorus ligand complex compound catalyst with in by the non-water aldehyde reaction medium of the free phosphorus ligand of solubilising, react with carbon monoxide and hydrogen, wherein this aldehyde reaction condition comprises, temperature of reaction is 45 to 200 ℃, and the total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated compounds is for being lower than 500psia (pound/inch ²), carbon monoxide pressure of tension is 1 to 120psia, hydrogen partial pressure is 10 to 160psia, and every mole of rhodium that wherein said reaction medium contains in described medium has total free phosphorus ligand of 2 moles, its improvements comprise that using a kind of general formula is

Single phosphatization tertiary phosphine metal-salt as the phosphorus ligand and the described free phosphorus ligand of described complex compound catalyst, each R group is represented a group that is selected from alkyl, aryl, alkaryl, aralkyl and cycloalkyl that contains 1 to 30 carbon atom respectively in the formula; The M representative is selected from a kind of metallic cation in basic metal and the alkaline-earth metal in the formula, and the value of n is 1 or 2 in the formula, is equivalent to the valence mumber of the concrete metallic cation of M representative; What wherein said aldehyde reaction medium also contained at least a q.s adds the organic solubilized agent, and it can make used rhodium-single sulfonation tertiary phosphine metal-salt ligand complexe catalyzer and free list phosphatization tertiary phosphine metal-salt ligand be dissolved in the described aldehyde reaction medium; Wherein said organic solubilized agent be selected from molecular-weight average be at least 150 alkylene oxide oligopolymer, molecular-weight average be at least organic nonionogenic tenside list alcohol of 300, molecular-weight average less than 150 and Xi Erde Brant solubility exponent be at least 10 polar organic compound and their mixture; Its condition is when they are present in the aldehyde reaction medium, the amount of described alkylene oxide oligopolymer is no more than 35% of above-mentioned medium-weight, the amount of described organic nonionogenic tenside list alcohol is no more than 60% of described medium-weight, and the amount of described polar organic compound is no more than 60% of described medium-weight; And additional condition is that the total amount that is present in the organic solubilized agent that adds in the described medium is no more than 60% of described medium-weight.

2, according to the process of claim 1 wherein in non-water aldehyde reaction medium, to also have high boiling aldehyde condensation by-product, wherein carbon monoxide pressure of tension be 3 to 90psia and wherein hydrogen partial pressure be 20 to 100psia.

3, according to the method for claim 2, wherein olefinically unsaturated compounds is the alhpa olefin of a kind of 2-5 of containing carbon atom, wherein each R group is represented a kind of group that is selected from branched-chain alkyl, phenyl and the cyclohexyl that contains 3-9 carbon atom separately, and wherein temperature of reaction is 60 ℃ to 130 ℃.

4, according to the method for claim 3, wherein each R group is represented a phenyl or cyclohexyl separately.

5, according to the method for claim 4, wherein alhpa olefin is propylene or butene-1.

6, according to the method for claim 4, M wherein ⁺Represent a kind of basic metal that is selected from lithium, sodium, potassium, caesium and the rubidium, and wherein n equals 1.

7, according to the method for claim 4, M wherein ⁺Represent a kind of alkaline-earth metal that is selected from calcium, barium, magnesium and the strontium, n equals 2.

8, according to the method for claim 6, M wherein ⁺Be sodium, and each R group is represented a phenyl.

9, according to the method for claim 6, M wherein ⁺Be sodium, and each R group is represented a cyclohexyl.

10, according to the method for claim 6, M wherein ⁺Be sodium, a R group is represented phenyl, and another R group is represented cyclohexyl.

11, according to the method for claim 3, in the time of wherein in being present in the aldehyde reaction medium, the amount of described alkylene oxide oligopolymer is no more than 30% of this medium-weight, the amount of described nonionogenic tenside list alcohol is no more than 50% of this medium-weight, and the amount of described polar organic compound is no more than 35% of this medium-weight, additional restricted condition is that the total amount that is present in the organic solubilized agent that adds in this medium is no more than 50% of this medium-weight.

12, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of alkylene oxide oligopolymer.

13, according to the method for claim 12, wherein alkylene oxide oligopolymer is the derivative that is selected from the polyethylene oxygen of poly-(ethylene oxide) ethylene glycol, poly-(third alkylene oxide) ethylene glycol and glycerol, and their mixture.

14, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of organic nonionogenic tenside list alcohol.

15, according to the method for claim 14, a kind of alkoxyl alcohol of wherein organic nonionogenic tenside list alcohol expression.

16, according to the method for claim 15, wherein alkoxyl alcohol is an ethoxy alcohol.

17, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of polar organic compound.

18, according to the method for claim 17, wherein polar organic compound is to be selected from methyl alcohol, Virahol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, benzene nitrile and tetramethylene sulfone.

19, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of mixture of alkylene oxide oligopolymer and organic nonionogenic tenside list alcohol.

20, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of mixture of alkylene oxide oligopolymer and polar organic compound.

21, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of mixture of organic nonionogenic tenside list alcohol and polar organic compound.

22, according to the method for claim 4, the organic solubilized agent that wherein adds is a kind of mixture of alkylene oxide oligopolymer, the pure and mild polar organic compound of organic nonionogenic tenside list.

23, according to the method for claim 2, wherein olefinically unsaturated compounds is a kind of alhpa olefin that contains 6 to 20 carbon atoms.

24, according to the method for claim 23, wherein alhpa olefin contains 6 to 14 carbon atoms, wherein each R group is represented a kind of a kind of group that is selected from branched-chain alkyl, phenyl and the cyclohexyl that contains 3 to 9 carbon atoms separately, wherein temperature of reaction is 60 ℃ to 130 ℃, and wherein the total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated compounds is 140psia or is lower than 140psia.

25, according to the method for claim 24, wherein each R group is represented phenyl or cyclohexyl separately.

26, according to the method for claim 25, M wherein ⁺Represent a kind of basic metal that is selected from lithium, sodium, potassium, caesium and the rubidium, wherein n equals 1.

27, according to the method for claim 25, M wherein ⁺Represent a kind of alkaline-earth metal that is selected from calcium, barium, magnesium and the strontium, and n equals 2.

28, according to the method for claim 26, M wherein ⁺Be sodium, and each R group is represented a phenyl.

29, according to the method for claim 26, M wherein ⁺Be sodium, and each R group is represented a cyclohexyl.

30, according to the method for claim 26, M wherein ⁺Be sodium, a R group is represented phenyl, and another R group is represented cyclohexyl.

31, according to the method for claim 23, in the time of wherein in being present in the aldehyde reaction medium, the amount of described alkylene oxide oligopolymer is no more than 30% of this medium-weight, the amount of described nonionogenic tenside list alcohol is no more than 50% of this medium-weight, and the amount of described polar organic compound is no more than this medium-weight 35%; Additional condition is that the total amount that is present in the organic solubilized agent that adds in this medium is no more than 50% of this medium-weight.

32, according to the method for claim 25, the organic solubilized agent that wherein adds is a kind of alkylene oxide oligopolymer.

33, according to the method for claim 32, wherein alkylene oxide oligopolymer is to be selected from the derivative of polyethylene oxygen of poly-(ethylene oxide) ethylene glycol, poly-(third alkylene oxide) ethylene glycol and glycerol and their mixture.

34, according to the method for claim 25, the organic solubilized agent that wherein adds is a kind of organic nonionogenic tenside list alcohol.

35, according to the method for claim 34, a kind of alkoxyl alcohol of wherein organic nonionogenic tenside list alcohol expression.

36, according to the method for claim 35, wherein alkoxyl alcohol is a kind of ethoxy alcohol.

37, according to the method for claim 25, the organic solubilized agent that wherein adds is a kind of polar organic compound.

38, according to the method for claim 37, wherein polar organic compound is to be selected from methyl alcohol, Virahol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, benzene nitrile and tetramethylene sulfone.

39, according to the method for claim 25, the organic solubilized agent that wherein adds is a kind of mixture of alkylene oxide oligopolymer and organic nonionogenic tenside list alcohol.

40, according to the method for claim 25, the organic solubilized agent that wherein adds is a kind of mixture of alkylene oxide oligopolymer and polar organic compound.

41, according to the method for claim 25, wherein adding the organic solubilized agent is a kind of mixture of organic nonionogenic tenside list alcohol and polar organic compound.

42, according to the method for claim 25, wherein adding the organic solubilized agent is a kind of mixture of alkylene oxide oligopolymer, the pure and mild polar organic compound of organic nonionogenic tenside list.

43, according to the method for claim 23, wherein hydroformylation process comprises that a kind of successive contains the circulating process of the catalyzer of liquid.

44, a kind of non-water hydroformylation process of producing aldehydes, this method comprises makes the alpha-olefin that contains 2 to 5 carbon atoms, contain alkene unsaturated organic compound, aldehyde product, by the rhodium of solubilising-phosphorus ligand complex compound catalyst with in by the non-water aldehyde reaction medium of the free phosphorus ligand of solubilising, react with carbon monoxide and hydrogen, wherein this aldehyde reaction condition comprises, temperature of reaction is 45 to 200 ℃, and the total gas pressure of hydrogen, carbon monoxide and the unsaturated mixture of alkene is lower than 500psia(pound/inch ²), carbon monoxide pressure of tension is 1 to 120psia, hydrogen partial pressure is 10 to 160psia, and every mole of rhodium that wherein said reaction medium contains in described medium has total free phosphorus ligand of 2 moles, its improvements comprise that using a kind of general formula is

Single sulfonation tertiary phosphine metal-salt as the phosphorus ligand and the described free phosphorus ligand of described complex compound catalyst, the M representative is selected from sodium in the formula, a kind of metallic cation in lithium and the rubidium, the organic solvent of wherein said complex compound catalyst and described free ligand can be selected from aldehydes high boiling point aldehyde condensation by-product and their mixture, and wherein said hydroformylation process is to carry out under the condition that no any organic solubilized agent of adding exists, and the agent of this kind organic solubilized is to be selected from molecular-weight average to be at least 150 alkylene oxide oligopolymer, molecular-weight average is at least organic nonionogenic tenside list alcohol of 300, molecular-weight average less than 150 and Xi Erde Brant dissolving index be at least 10 polar organic compound, and their mixture.

45, a kind of non-water hydroformylation process of producing aldehydes, this method comprise make the alkene unsaturated organic compound that contains 2 to 20 carbon atoms contain alkene unsaturated organic compound, aldehyde product, by the rhodium of solubilising-phosphorus ligand complex compound catalyst with in by the non-water aldehyde reaction medium of the free phosphorus ligand of solubilising, react with carbon monoxide and hydrogen, wherein this aldehyde reaction condition comprises, temperature of reaction is 45 to 200 ℃, and the total gas pressure of hydrogen, carbon monoxide and the unsaturated mixture of alkene is lower than 500psia(pound/inch ²), carbon monoxide pressure of tension is 1 to 120psia, hydrogen partial pressure is 10 to 160psia, and every mole of rhodium that wherein said reaction medium contains in described medium has total free phosphorus ligand of 2 moles, its improvements comprise that using a kind of general formula is

Single sulfonation tertiary phosphine metal-salt as the phosphorus ligand and the described free phosphorus ligand of described complex compound catalyst; R group is represented cyclohexyl and another R group is represented phenyl or cyclohexyl in the formula, and wherein the M representative is selected from a kind of metallic cation in basic metal and the alkaline-earth metal, and the value of n is 1 or 2, is equivalent to the valence mumber of the concrete metallic cation of M representative; Wherein the organic solvent as described complex compound catalyst and described free ligand can be selected from aldehyde, high boiling point aldehyde condensation by-product and their mixture, wherein said hydroformylation process is to carry out under the condition that no any organic solubilized agent exists, and this kind solubilizing agent be selected from molecular-weight average be at least 150 a kind of alkylene oxide oligopolymer, molecular-weight average be at least a kind of organic nonionogenic tenside list alcohol of 300, molecular-weight average less than 150 and Xi Erde Brant solubility exponent be at least 10 polar organic compound and their mixture.